CN100441407C

CN100441407C - Treated textile substrate and method for making a textile substrate

Info

Publication number: CN100441407C
Application number: CNB2004800428146A
Authority: CN
Inventors: Y·王; D·T·麦克布雷德; R·S·科尔曼
Original assignee: Milliken and Co
Current assignee: Milliken and Co
Priority date: 2004-02-24
Filing date: 2004-09-27
Publication date: 2008-12-10
Anticipated expiration: 2024-09-27
Also published as: US7213309B2; US8541056B2; US20100218878A1; CN1942311A; US20050186872A1; US20070204444A1

Abstract

Compositions and methods for treating textile substrates to obtain superior liquid repellent properties are disclosed. Durable microscopic surface structures imparted to the fibrous substrate allow liquids to bead up and roll off of its surface. Mechanical abrasion or sanding techniques may be used to create the microscopic surface structures on the surface of a fibrous textile substrate, without substantially breaking fibers, followed by a chemical treatment using, for example, fluorocarbon-containing repellent compositions. Particles may be employed in combination with repellent compositions to achieve superior repellent properties. A property of the roughened surface fibers, the Roughness Factor, is used to characterize the microscopic surface structures on the treated textile surface. Treated textile substrates are disclosed which achieve superior water and oil repellency, even after multiple abrasion or laundering cycles.

Description

Treated textile substrates and manufacturing textile substrates method

Background technology

In recent years, people have keen interest to relevant so-called super water proofing property surface and its " self-cleaning performance " in surface chemistry and the textile field.The main liquid body of automatically cleaning effect (normally water) of this super water-proof surface is controlled with the interaction on the surface of for example textile substrates.Interaction between liquid, air and the smooth surface of solids is by Young's equation (Young ' s equation) decision, and describes with the contact angle between the drop and the surface of solids usually.Contact angle is decided by the surface tension between solid-liquid, solid-gas and liquid-gas interface.The surface of solids can be, for example, and not (do not have or do not have water absorbing capacity) of hydrophilic (glassware for drinking water is had strong affinity or has water absorbing capacity) or water proofing property to the affinity of water.Usually, the surface more waterproof of the surface ratio with big contact angle with less contact angle.Young's equation and solid-liquid surface contact angle schematic diagram are as shown in Figure 1.

Young's equation can be used for determining the contact angle of drop (for example, water) on even flat surface.Up to now, for

The fluorinated material of face energy, the maximum water contact angle on the smooth surface of solids are about 120 degree.For further increasing contact angle, need carry out the surface texture modification.Contact angle on the known rough surface with identical chemical property is much higher than the contact angle on the flat surface.For the high coarse water-proof surface with relative high aspect ratio (its allow catch under water droplet a large amount of air), contact angle can be greater than 150 degree (that is, super water proofing property surface).In all having two kinds of situations of rough surface, owing to the surface area that contacts with water droplet has changed, so Young's equation has been changed.When water droplet was dripped on so super water proofing property surface, water droplet was collected together glomeration, can tumble when the surface tilts a little.But, be noted that in order to obtain the little digression (it is defined as the minimal tilt angle of water droplet when beginning to roll) of rolling, be not enough only according to high contact angle.Also need little contact angle hysteresis amount (hysteresis) (its be defined as between advancing angle and the receding angle poor).Advancing angle is to increase observed liquid contact angle when being pressed in lip-deep droplet size with syringe for example.What obtain when reducing the volume of same drop is receding angle.If drop has big advancing angle, but have quite little receding angle (that is, having sufficient contact angle hysteresis amount), drop may be collected together into the globule, but the drop rolling needs the bigger digression of rolling.And, on the surface of drop process, can stay the liquid mark.On the other hand, if drop not only has big advancing angle but also have big receding angle, then do not have hysteresis substantially, drop can be collected together glomeration, and with little angle of inclination roll from and can not stay tangible liquid mark (promptly super water proofing property surface) on the surface of its process.This globule and the rolling action collected together into can make drop roll from the surface and take away loose dirt or dust thereupon, and this just forms " automatically cleaning " performance.On the other hand, have on the smooth surface of less contact angle, drop can not be taken away surperficial dirt.It can only make the dirt redistribution usually.Fig. 2 has schematically provided these scenes.

It is found that at occurring in nature, the water loving plant that is called as lotus has this super water proofing property self cleaning method.Nelumbium is the wetland species that originate from the Asia, and does not dye because it goes out mud and be called pure symbol by being respected.The super waterproof self-cleaning property of nelumbium is from the combination of coarse physics surface texture and water-proof surface chemical property.Particularly, the lotus leaf surface presents two kinds of other surface irregularities of level, as shown in Figure 3.The surface of every leaf (also can referring to Fig. 3 A and 3B) all by a collection of about 5 to 10 microns high and at interval 10 to 15 microns small embossment cover.In these three figure, obviously demonstrate 20 microns engineer's scale, this feasible approximate size that can estimate surface characteristics.This organizes irregular surface texture and also is measured as the anti-crystalline of little many wax shapes that diameter is less than or equal to about 1 nanometer and covers.Can think that this two-layer configuration on the lotus leaf has increased the roughness on whole surface, this has correspondingly increased its water proofing property.Two-layer configuration with waterproof " paddy " reduced from, for example, the water of condensation, evaporation or torrential rain is invaded the possibility of surperficial air layer, because it is unfavorable for that very water is full of above-mentioned paddy.Therefore can think that the physical surface structure of lotus leaf combines with its surface chemistry (waterproof wax crystal), makes its surface can be used as super water proofing property self-cleaning surface, here water can collect together glomeration roll from, and take away loose dirt from the surface.This super waterproof automatic cleaning action in the presence of surface water is commonly called " lotus leaf effect ".

Similar to nelumbium, repel the textile surface that liquid and proof have super water proofing property and relevant self-cleaning performance and also can more effectively keep its outward appearance.Therefore, having to the textile surface of the similar performance of nelumbium can be high expectations.Textile substrates with lotus leaf performance can be used for making high waterproof and/or anti-liquid spot fabric, and these fabrics can be used for for example purposes such as rainy day equipment, ship cover, rain cover, outdoor furniture, clothes.Waterproof that is provided and/or anti-liquid spot fabric can also prevent bacterium and fungus growth, because water and/or other liquid often can not assemble or wick in such surface, thereby can not provide breeding ground for bacterium and mould.

The protection type textile substrates sometimes can obtain on market.For example, known fluorocarbon is handled and can be provided protective finish for such substrate.Known many compositions that contains fluorocarbon are coated on the textile substrates waterproof and grease proofness can be provided.But, for obtaining the required big contact angle of super water-proof surface and roll digression for a short time, usually need the surface texture similar to lotus leaf.People carry out various effort to make lotus leaf sample surface texture, the U.S. Pat 6 of Shouji etc. for example, 068,911, the U.S. Patent Application Publication Nos.2002/0150723,2002/0150724,2002/0150725,2002/0150726,2003/0013795,2003/0147932 of the U.S. Patent Application Publication No.2002/0016433 of Keller etc. and Creavis Gesellschaft Fuer Techn.Und Inovation MBH.These documents disclose the method for using particulate to construct coarse structure on essentially smooth flat surface.The textile substrates of handling according to these documents can't provide lasting protective, because it is through being everlasting when washing or lose most or all of protectives when during normal use denuding.Therefore, those textile substrates that still keep the favourable anti-fluidity of excellence after through the abrasion in washing or normal the use be expect very much with novelty.

The U.S. Patent No. 5,968,642 of Saito relates to a kind of goods with water proofing property fluorine resin surface.These goods have the water proofing property fluorine resin surface of being made up of irregular porous material, and this material is not more than 40 microns fluorine resin particle by average grain diameter and piles up mutually brokenly and form.And this patent also relates to the substrate with flat surface, for example, and aluminium flake.In addition, this patent is not demonstrated it in the applicability that has on the composite construction textile substrates of irregular surface, does not show the durability of this inorganic agent to washing and textile application abrasion yet.

The U.S. Pat 6,649,266 of Gross etc. relates to the substrate such as glass or metal that has the microstructure surface that is used for system easy to clean, and the method for making these substrates.Inorganic agent is made of the composition of the condensate that comprises one or more hydrolyzable compounds (condensate).It is 10: 1 to 1: 2 hydrolyzable groups and non-hydrolysable group that at least a portion in these compounds contains proportional simultaneously.Before being coated to coating composition on the substrate, use inorganic nanoparticles to form the microstructure surface.The microstructure surface can also by dry and/or solidify before or among, coating composition is pressed.The contact angle of water or cetane is than big at least 5 degree of the contact angle on the corresponding smooth surface on this microstructure substrate.Though disclosed method can well be used on flat surface in this patent, instruction wherein and undeclared applicability on the composite construction textile substrates do not illustrate the durability of this processing to the abrasion in washing and the typical textile application yet.

The U.S. Patent application No.2003/0096083 of Morgan etc. relates to the surface of object (in particular for receiving the container of liquid), comprises the very surface of waterproof, also relates to the method for making this kind surface.According to the document, this surface texture is to make like this: thin sandblast is carried out on the surface and/or used suitable embossing step to carry out embossing with suitable sand-blast material, or use suitable etching material to carry out etching.The document is not instructed textile substrates how to handle composite construction, and also undeclared this inorganic agent is to the durability of the abrasion in washing and the typical textile application.

One piece of public announcement of a patent application WO 01/75216 discloses the method for using finish layer (finishing layer) on the textile carrier material.Open according to this patent application, on the carrier material of a group of fiber, tissue and fabric, use waterproof or anti-oil reservoir.Waterproof or oil resistant finish layer comprise at least two kinds of waterproof or anti-oil ingredient.First component comprises at least a dispersant, and second component comprises at least one decentralized photo or colloid.Dispersant and decentralized photo exist with gel state.The colloid of decentralized photo is dispersed in the dispersant by following approach in anisotropic mode: colloid is present in conc forms in the zone on arrangement surface, and it forms the phase boundary layer between finish layer and the surrounding atmosphere.The essential characteristic of this method is to use decentralized system to make host and guest (guest-host) system, and this system can allow the finishing agent component to carry out the space self assembly." visitor " component is called the phase that sub-argument is come out from " master " component, and is enriched in the finish layer top on the micro-rough surface with column structure.This method depends on the phase instability of chemical mixture inherence.Therefore, technology is difficult to control, and may cause problem in extensive manufacture process.

Another patent application is open, WO 02/084016 relates to the smooth textile constructions with automatically cleaning water-proof surface, its by (a) at least a synthetic and/or natural textile basic material A and (b) a kind of have projection that particulate causes and depression, artificial, to the surface of small part waterproof, above-mentioned particulate under the situation of not using adhesive, resin or lacquer securely attached to basic material A on.Above-mentioned smooth textile constructions obtains by following manner: the solvent with at least a particulate that contains insoluble form is handled basic material A, removes then and desolvates so that to small part particulate securely on the surface attached to basic substance A.But this patent application discloses undeclared little dynamics and rolls angle and the durability to washing and denuding.

The open WO 02/084013 of another patent application relates to the polymer fiber with automatically cleaning water-proof surface, its by (a) at least a composite fibre materials A and (b) a kind of have projection that particulate causes and depression, artificial, to the surface of small part waterproof, above-mentioned particulate under the situation of not using adhesive, resin or lacquer securely attached to basic material A on.This polymer fiber can obtain by following manner: the solvent with at least a particulate that contains insoluble form is handled fibrous material A, remove then desolvate so that to the small part particulate with the surface of fixed form attached to composite fibre materials A.But this patent application openly and the little dynamics of art explanation is rolled the angle and to the durability of washing and abrasion.

On film, metal or ceramic surface, use water proofing property particulate and adhesive in solvent system to have significant disadvantages with the prior art systems that realizes super waterproof self-cleaning performance, for example, poor durability when being applied to the yarn fabric substrate.During normal the use, the coating that is applied in the surface grinds off easily.Fig. 4 and Fig. 4 A have shown the fiber in the woven textile substrates that the method described among the U.S. Patent application No.2002/0016433 A1 according to Keller etc. handles with the waterproof particulate.These textile substrates can obtain protective to a certain degree, but this protective is not durable concerning the washing of fiber or textile substrates.The waterproof particulate undesirably grinds off from the surface easily.

In a word, as described herein, most of prior art of attempting to obtain the lotus leaf effect all relates to the have smooth smooth surface substrate of (for example glass, pottery, sheet metal and plastic foil etc.).On such smooth surface, the required coarse structure of super waterproof self-cleaning performance can be only by using particulate to obtain.On typical textile substrates (for example woven fabric), there is the complex surfaces pattern.For example, the structure of mm-scale produces by the braiding of yarn; The structure of 10 to 100 micro-meter scales forms by the fiber of yarn inside.In addition, textile substrates also has mechanical flexibility.On the flexible textile substrate of such labyrinth, typically only use particulate to be not enough to construct and show the lotus leaf effect and use caused abrasion to have the expection coarse structure of durability to washing with by textile.

Can give the textile substrates surface texture by other method.For example, it is known handling textile surface with mechanical means.Use comprise to textile denude, the processing of the technology of sand washing or napping can provide good hand feeling (or sensation) or other performance as fabric.But the common purpose on mechanical treatment textile substrates surface is to make fibrous fracture, makes the soft filoplume of fabric face with generation.Therefore, the purpose of these traditional mechanical treatments is normally improved the feel of substrate, rather than makes the coarse and don't fracture of fiber surface.For example, United States Patent(USP) Nos. 6,112,381,5,815,896,4,512,065,4,316,928 and 4,468,844 have described the various mechanical treatments that are used for the textile substrates surface.But, find that the substrate that carries out mechanical treatment with these technologies all lacks the Ideal Rough Surface that the lotus leaf responsiveness can be required.

Therefore, need composition and/or method a kind of textile substrates that can cause having super waterproof self-cleaning surface, processing or coated substrate.The method that the surface texture of the surface nature that shows height protective (roll as little dynamics angle (DRA) measured) will be provided and handle textile substrates is expected.Will provide the surface texture of the processing yarn fabric substrate that shows height protective (after repeatedly washing and/or denuding, being durable) and the method for processing yarn fabric substrate also to expect.

Surprisingly, we find, on structure complicated textile substrates like this, by (for example mechanically making part fiber textile substrate surface, more than or equal to 10%) roughening and do not interrupt fiber basically, can access excellent anti-liquid (for example, water or oil) performance.After mechanically handling substrate, re-use the protection component that for example contains fluorocarbon it is carried out chemical treatment, can strengthen the durability of barrier propterty.Particulate can be used in combination with the protection against chemical inorganic agent.Mechanically roughened processing of the present invention is different fully with prior art in processing procedure.Resulting treated textile substrates is considered to that the abrasion that stands in circulation cleaning repeatedly and/or normal the use is had durability, because the mechanically roughened structure on the fiber surface is the part of fiber itself, it is connected on the fiber lastingly and directly.

Description of drawings

Fig. 1 shows contact angle phenomenon and wetting schematic diagram;

Fig. 2 is the figure that is presented at drop behavior contrast on rough surface and the smooth surface;

Fig. 3 is the microphotograph that shows super waterproof " coarse " structure of the lotus leaf with microstructure and little many nanostructureds;

Fig. 3 A has shown the microphotograph of amplification of the two-layer configuration of lotus leaf shown in Figure 3;

Fig. 3 B has shown the side pattern of the surface imperfection of the lotus leaf shown in Fig. 3 A;

Fig. 4 has particulate to form nanostructured but also show 1000 times of zoom microscope photos of prior art fiber of the durability of relative mistake on the surface;

Fig. 4 A is the side corresponding to the prior art fiber of Fig. 4;

Fig. 5 is the zoom microscope photo of the plain weave polyester textile of embodiment 10 descriptions, has shown the relative low second area with roughness in the high relatively first area of roughness;

Fig. 5 A is 500 times of zoom microscope photos that shown the first area with the high relatively surface fiber of roughness;

Fig. 5 B is 500 times of zoom microscope photos that shown the second area with the low relatively surface fiber of roughness;

Fig. 5 C is 50000 times of zoom microscope photos that illustrate Fig. 5 of the single nanoparticle that the high relatively fiber surface of roughness exists;

Fig. 5 D is 50000 times of zoom microscope photos that illustrate Fig. 5 of the nanoparticle agglomerate that the high relatively fiber surface of roughness exists;

Fig. 6 is the plain weave polyester textile that carries out mechanical treatment by traditional corase grind roller, and it illustrates the fiber that has a large amount of fractures on fabric face;

Fig. 7 A-7C is the zoom microscope photo of the tent fabric fiber that further describes in embodiment 6, and this fiber has the height rough edge of the coefficient of roughness that can be used for measuring these fibers;

Fig. 7 D has shown the profile or the shade of the estimation of the coefficient of roughness (R.F.) that is used to measure fiber shown in Fig. 7 C;

Fig. 7 E has shown the side profile figure of fiber shown in Fig. 7 C;

Fig. 8 A is the microphotograph of 1000 times of amplifications of embodiment 20 described tent fabric fibers, and it is selected from the high relatively zone of roughness and determines to have the corresponding high coefficient of roughness;

Fig. 8 B has shown the side profile figure of the rough wearing fiber of Fig. 8 A, and it can be used for estimating the coefficient of roughness of fiber;

Fig. 9 A is 50 times of zoom microscope photos of embodiment 10 described plain weave polyester textiles, has shown the relative low second area with roughness in the first high relatively district of roughness (mechanically roughened part);

Fig. 9 B has shown the image identical with Fig. 9 A, except the coarse zone of textile substrates apparent height doubly is made as black (pixel value is 0);

Fig. 9 C has shown the image identical with Fig. 9 B, except the pixel in the coarse zone of the height of representing the textile substrates surface is set to 255 (i.e. whites), and the pixel value of remainder is set as 0 (being black), and like this, image is converted into has only black and white binary image.

Summary of the invention

Now, with reference to each embodiment of the present invention, list one or more embodiment below.Each embodiment is all explaining that mode of the present invention provides, rather than restriction the present invention.In fact, for a person skilled in the art, under the situation that does not depart from scope of the present invention or spirit, the present invention is made various improvement and modification is conspicuous.All patents of mentioning in the present patent application, disclosed patent application and any other publication are all introduced reference here in full.

As previously mentioned,, should on this surface, set up desired surface roughness, preferably have high aspect ratio for obtaining the surface of super anti-liquid.The air of being caught by the paddy on the rough surface can make drop collect together glomeration and roll from the surface.A content of the present invention is to make the method for rough surface on the textile substrates of imitation lotus leaf.The invention provides composition and the method for handling textile, it provides excellent anti-fluidity and potential performance easy to clean and washing and abrasion is had durability for textile substrates.

Roughness is generally defined as and comprises any projection, indentation, ditch, wearing and tearing, breach, hole or other surface texture that exists on the fiber textile substrate surface, these are results of mechanical treatment, chemical treatment or its combination, and above-mentioned processing is relative so smooth and irregular surface with the smooth relatively surface modification with rule.Accordingly, descriptive term " roughness " typically refers to these surface textures that exist on the single fiber surface, and wherein, these surface textures are positioned at the normal direction of fiber axis substantially.Descriptive term " surface texture " can also be used for describing rough features with " roughness " exchange." microscopic surface texture " on the term fiber surface typically refers to size those surface textures less than fibre diameter.The size of these microscopic surface textures is less than 100 microns usually.

Can give the fiber surface roughness with adding formula (additive) or subtracting formula (subtractive) method.Many trials of setting up coarse structure all are to go up the method for adding various particulates by using on surface (comprising textile surface) in the prior art.For using the coarse structure of particulate, should use the small particle of big particulate or high concentration from the teeth outwards at fiber surface manufacturing high aspect ratio.No matter the sort of situation is difficult to only depend on the fiber textile substrate of some smooth pliable and uses particulate to obtain lasting high aspect ratio surface.Particulate is often by abrasion or alternate manner and easily removed from the surface.

Perhaps, can in subtracting the formula method, adopt mechanical treatment, chemical treatment or its combination so that remove or redistribute material, thereby obtain microscopic surface texture from the textile substrates surface.Subtracting the formula method, to make the advantage of roughness be that the coarse microstructure of fiber surface is connected on the treated textile substrates surface and is its a part.Roughening (roughen) textile substrates surface can be called as " whole " in this way, because roughening can not cause adding new and different materials on the fiber of textile substrates.Rough surface and not the chemical composition on the surface of roughening (that is, not having new material suitably joins on the fiber or the surface of textile substrates) can not take place suitably to change owing to treatment process.

In the present invention, can preferably adopt to use to subtract the formula method and make textile surface mechanically roughened, thereby excellent anti-fluidity energy is provided so that give whole microscopic surface texture as textile substrates.Because mechanically roughened surface texture has globality, it is difficult for being worn away or washing off in washing or normal the use.Therefore, the integral surface roughness, perhaps whole microscopic surface texture can strengthen the durability of textile substrates barrier propterty.Normally textile substrates opposing friction and repeated washing in normal use is necessary for this durability.For explaining this purpose, Fig. 5 A has explained the relative high scope of said whole roughness here with 8A.

In an embodiment of the invention, roughness can obtain by following manner: according to the technology that hereinafter will describe in more detail, make the textile substrates surface mechanically roughened, so that obtain high anti-fluidity textile substrates.In this embodiment, can give the microscopic surface texture of at least one size range for the fiber surface of textile substrates.In another embodiment, applied chemistry protective agent and mechanical treatment can be used in combination to obtain the textile substrates of high anti-fluidity energy.In another embodiment of the present invention, before the applied chemistry protective agent, afterwards or simultaneously, can add diameter on mechanically roughened textile surface is the particulate that nanometer arrives micron-scale, to form the high liquid textile substrates surface of preventing.In this embodiment, the rough surface structure with at least two different size scopes is endowed the fiber surface of textile substrates.Above-mentioned size range can not comprise mutually that such two size ranges can be not overlapping, and perhaps changing scope can have a certain overlapping.These embodiments will be described hereinafter in more detail.

For the present invention, the method for making high anti-liquid rough surface is applicable to textile substrates widely.Textile substrates can be fibrous textile substrates, for example, and woven, knitting or nonwoven, or striped scrim.These fibrous textile substrates can be combined together to form composite construction in any way.Composite construction can comprise other material, for example, and film, coating, foam, enhancing substrate, adhesive etc.The multilayer of composite construction can use the means such as but not limited to adhesive, heat lamination and combination thereof to combine.

Fiber in the fibrous textile substrates can be formed by following fiber: for example, and the staple fibre of synthetic fibers, natural fiber, use natural component or its combination.Synthetic fibers comprise, such as but not limited to, polyester, acrylic acid, polyamide, polyolefin, aromatic polyamides, polyurethane, regenerated cellulose and blending thereof.In particular, polyester comprises, for example, and PETG, poly terephthalic acid Sanya phenylester, polybutylene terephthalate (PBT), PLA and combination thereof.Polyamide comprises, for example, and nylon 6, nylon 6,6 and combination thereof.Polyolefin comprises, for example, and polyethylene, polypropylene and combination thereof.Aromatic polyamides comprises that for example, poly-p-phenyleneteraphthalamid (that is,

), poly-m-phenyleneteraphthalamid (that is,

) and combination.Natural fiber comprises, such as but not limited to, wool, cotton, linen thread and yarn, ramie, jute, flax, silk, hemp and blending thereof.The artificial material of exemplary use natural component comprises regenerated cellulose (being viscose glue), lining Olympic Competition fiber (lyocell) or its blending.

Textile substrates can be formed by the fiber or the yarn of arbitrary dimension, comprises little danier (microdenier) fiber and yarn (every ultimate fibre is less than the fiber or the yarn of 1 danier).Fiber or yarn can be by short fiber, long filament, bicomponent fibres, split release bicomponent fibre or blending is formed.Fiber can comprise slit fibre or flat filament.

As previously mentioned, a kind of method of giving the whole roughness of textile substrates is by mechanical face finishing.With regard to purpose of the present invention, term " face finishing " (face-finishing orface-finished) is meant, for example, pass through method and technology that the patent quoted and patent application describe in open and come the surface of snag, sand washing, sandblast, roughening or mechanical alteration textile substrates.For example, U.S. Pat 6,112,381,5,815,896,4,512,065,4,316,928 and 4,468,844 each self-described the various mechanical face finishing methods that are used for textile substrates.The example of these mechanical face finishing technology, comprise, for example, with (for example scribbling abrasion with sand grains, diamond, carborundum, silica, alundum (Al, titanium carbide, tungsten carbide etc.) device (for example, roller) sand washing or snag, particulate spraying (for example, sandblast), substrate is exposed in the high temperature fluid of water for example or air or the like.For the present invention, above-mentioned all face finishing technology and change the use that all can separately or combine are so that make the textile substrates surface roughening and make microscopic surface texture on the surface of institute's fibre-bearing therein.To these changes in technology or revise and to comprise and allow to make the surface roughening of textile substrates effectively and can not interrupt the wherein technology of contained a large amount of fibers.

Potential mechanical means preferred, nonrestrictive, the textile substrates face finishing comprises, makes textile substrates contact abrasive surface, and the relative textile substrates of this abrasive surface can be on quiet, vibration or rotation.Can cover sand paper, diamond or other abrasive particle on the abrasive surface.If use cylindrical rotation roller, it can be certain angle perpendicular to the length direction (promptly vertically striding across the width of textile substrates) of textile substrates or with the length direction of textile substrates and exist, thereby certain zone or the part on control textile substrates surface are subjected to more or less processing.For example, the woven fabric of specific use wishes that its warp thread rather than weft yarn are subjected to most of coarse processing most.In order to control such processing, various parameters that can adjusting process obtain desired values.These parameters comprise, for example, (a) the abrasion roller imposes on the tension force of textile substrates, (b) engaging pressure of abrasion roller, (c) the abrasion roller transmits the relative rotation speed of comparing with textile substrates, (d) the contact time of staying between abrasion roller and the textile substrates, and (d) abrasive size on the treatment tube.

Usually, traditional face finishing technology is used to give fabric some characteristic, for example, and the wicking of the feel that more needs (comprising the soft surface degree), the drapability of improving fabric, improvement fabric etc.In order to give textile substrates these characteristics, conventional art (using the rotation abrasion roller of 400 granularities or rugosity) is through being usually used in deliberately making fibrous fracture, and produces weak point, dense area fracture or loose fibres of " filoplume " that can increase the yarn fabric substrate surface.With regard to purpose of the present invention, the filoplume that increases on these broken fibers and the substrate is considered to the negative characteristics of textile substrates, because the fiber of fracture can be considered to the fiber that stretches out from the surface of textile substrates, it may become liquid and roll obstacle from the surface.Therefore, the substrate that has many broken fibers on the surface tends to reduce the protective of substrate.In fact, the broken fiber on can the identified surface pattern is because it demonstrates usually from textile surface outstanding clear and definite end or tip.It can also be differentiated by following manner: these fibers have left its initial position basically, so quite a lot of part of fiber is stretched from textile surface.This situation in back can take place in following situation: for example, can see on the image of woven fabric that fiber has left its initial yarn beam and crossed or enter different yarn beam.Before face finishing, staple fiber ends or tip clocklike appear at the surface of spun yarn, do not think the broken fiber with regard to the object of the invention usually.

Fig. 6 has shown the textile substrates of handling with the mechanical face finishing mode of tradition employing in the prior art.A large amount of broken fibers and/or long filament can be seen in surface at substrate 40.In fact, broken fiber is the principal character on surface.Therefore the scale that is shown as 1 millimeter can estimate the approximate size of surface characteristics significantly near the bottom of Fig. 6.Can calculate on the treated typical textile substrates every square millimeter broken fiber quantity in this way, find make when handling with corase grind erosion of the prior art, its quantity is about 9 to about 30.As previously mentioned, find that these long broken fibers that stretch out from the textile substrates surface are unfavorable for making super anti-liquid automatically cleaning textile substrates.Therefore, the mechanical face finishing of using usually in the prior art can not produce the textile substrates microscopic surface texture that helps super anti-fluidity.

For manufacturing has the textile substrates of super anti-fluidity, find that mechanical face finishing can be by unconventional mode to give substrate surface for roughness.As shown in Figure 5, the technology lighter (lighter) during the coarse level that face finishing technology used in the present invention can provide is used than traditional industry or meticulousr, thus make the fiber of yarn fabric substrate surface or long filament roughening and can not rupturing slightly.The method according to this invention is carried out the textile substrates surface of mechanical face finishing, as shown in Figure 5, is same as the substrate surface that usefulness shown in Figure 6 mode of the prior art is carried out mechanical face finishing far from.Therefore, when with the purpose of traditional face finishing technology relatively the time, use the ability of the super waterproof textile substrates of mechanical face finishing technology manufacturing to be considered to give the new and non-obvious method of textile substrates lotus leaf effect.

In order to obtain said processing of the present invention here, utilize following method: use by the very tiny abrasion roller of abrasion sand, abrasive grain or the mechanical face finishing of sand roller, wherein, scribbling abrasive grain on the roller is about 600 to about 1200 (grit) or littler abrasive particle.These abrasion rollers can make the roughening on a large scale of fiber surface and can not interrupt a large amount of fibers.Therefore, it can make gratifying whole microscopic surface texture on fiber surface, and this causes textile substrates to have lasting super anti-fluidity energy.According to the present invention, be unfavorable for making the broken fiber number that the quantity of the broken fiber of super anti-liquid self-cleaning property textile substrates observes on the textile substrates surface by traditional face finishing technical finesse.Observed broken fiber quantity is less than 5 pieces/square millimeter usually on treated substrate of the present invention, preferably is less than 3 pieces/square millimeter.In some cases, observe broken fiber can be substantially and textile substrates in the same plane, rather than stretch out from substrate surface.

According to purpose of the present invention, " in the plane of fibre-bearing substrate " or " in the textile substrates plane " can be explained by following discussion.Textile substrates is made into or is configured to sheet form usually.In use, textile substrates has the thin slice feature, is that the piecewise has at least.The fibre-bearing substrate plane can the local at least thin slice definition by textile substrates.In the operation, substrate can smoothed, corrugationless be placed on the smooth horizontal supporting face, and supporting surface can be used to define substrate plane.

The special distribution of rough surface structure of giving the textile substrates surface by the present invention instruction mechanically roughened is very characteristic, and is different from that other method gives.If for example, the fiber or the yarn that constitute textile substrates are roughened before forming textile constructions, will wish that rough surface structure evenly distributes on yarn or fiber.In contrast, cause the more uneven distribution of rough surface structure with the method for the present invention of abrasion roller processing textile substrates.

Particularly, for some textile substrates, fiber can form yarn beam.Tend to handle the bossing of textile substrates with abrasion roller mechanical treatment textile surface.According to keeping textile and the vertical that the abrasion treatment tube contacts, can handle the rat part of different amounts.Equally, textile substrates is carried out the fiber roughening that mechanical face finishing often can not cause yarn beam inside, because internal fiber often is subjected to being positioned at the protection of yarn beam outer fiber.In addition, fibrous textile substrates, for example, woven fabric also can all have rough surface structure at woven fabric ledge and/or sunk part feature (being warp thread bundle and/or weft yarn bundle), and the volume of fabric is additionally increased.

In addition, according to the angle and direction of abrasion roller, the fiber in the textile substrates on the different directions can be subjected to different processing.For example, the weft yarn in the many abrasion rollers of the prior art system preferred process machine-knitted structure.Therefore, when using the abrasion roller that textile surface is carried out when mechanically roughened, though the entire top of fiber textile substrate or lower surface can be processed, entire top or lower surface be roughening equably.According to the present invention, it is about 20% that treated textile substrates surface percentage is confirmed as average out to, disclosed in more detail as following embodiment part institute.Seeming may be surprisingly, only handle on the textile substrates surface relative fraction and can make the improvement of mystery like this anti-fluidity, but, this part surf zone that anti-fluidity is made huge contribution but is to contact with impact liquid the easiliest, and this surf zone mainly is the bossing that passes through mechanically roughened surface.The non-uniform Distribution of this roughness can appear in expectation on the surface of mechanically roughened woven, knitting, non-woven and striped plain weave linen-cotton textile substrates.The percentage of estimating to increase roughening part on the textile substrates can further improve anti-fluidity energy.

Textile substrates is carried out mechanically roughened processing rather than to forming being on the other hand that yarn before the substrate or fiber handle, can not be on the top surface of another point on the fabric at the fiber on the yarn top surface of a point on the fabric.Therefore, same fiber can be shaggy in the part of fabric, and do not have rough surface in another part.Therefore, when textile surface being carried out when mechanically roughened,, constitute the fiber of substrate surface or the whole surface of yarn and can not be roughened fully usually though the entire top of fiber textile substrate or lower surface can be processed with the abrasion roller.Therefore, the fiber of roughening can be only at its part periphery with only along its length direction roughening of part.Valuablely in high anti-fluidity is provided be, the part of roughening should have appropriate length (will contact the bossing of drop on the basic at least covering fabric), and the part of roughening should be in the position on vertical textile substrates surface substantially on the fibre circumference face.The surprisingly following fact: the whole surf zone of fiber that constitutes textile substrates only has part need handle so that high anti-fluidity to be provided.But the liquid on contact textile substrates surface often can not wicked into or be infiltrated height and be prevented in the yarn beam of fluidity textile substrates and further contact internal fiber.This understanding allows simpler and more economical processing method, and for example, that can implement simply denudes the roller processing to yarn fabric integral body, rather than the whole surface of handling every one thread or fiber, although this processing also is effective.

The roughness of fiber can quantitatively be determined according to the quantity of textile substrates, will be described in detail below.Generally speaking, although, if with microscope along the fiber of assigning to detect roughening away from any roughness of the seamed edge of broken fiber end or tip, can measure the profile length (mainly being shade) of roughening fiber so.Along the ratio of the length of the coarse profile of fiber and straight length as roughness (R.F.).Usually, according to the present invention, the roughness of the fiber of removing from treated textile substrates is equal to or greater than 1.10, below describes in detail.

Based on foregoing detailed description, the present invention can describe by following embodiment: the fibre-bearing substrate with first surface and second surface, has whole microscopic surface texture on its at least one surperficial at least a portion, wherein said microscopic surface texture has the projection on the plane that is basically perpendicular to described fibre-bearing substrate, described at least one surface is made of the part with a large amount of fibers that do not rupture substantially, it comprises the surface texture of the partial-length at least on the described fibre length direction, and the coefficient of roughness of wherein said fiber is more than or equal to about 1.10.More preferably the coefficient of roughness is more than or equal to 1.20, further is preferably greater than or equals 1.30.If backing material itself is not anti-fluidity, can prevent liquefaction processing to the fibre-bearing substrate.Usually, in order to obtain super anti-fluidity energy, the fibre-bearing substrate also can have at least 10% whole microscopic surface texture on its at least one surface.But, can more preferably on its at least one surface, have at least 15% whole microscopic surface texture, further preferably on its at least one surface, have at least 20% whole microscopic surface texture.

In the foregoing description, " be basically perpendicular to the plane of fibre-bearing substrate " and be meant that object (surface texture specifically) has the parts that stretch out or enter or be basically perpendicular to the suitable dimension of this substrate plane from fibrous substrate plane (defined as the front).For perpendicular to the textile substrates plane with strengthen anti-fluidity can projection, it should be positioned at the top surface or the contact surface of textile substrates.

In other embodiments, can be before using the protection component, afterwards or among at least one surface of fibrous substrate, add other particulate constituent to form the roughness of another kind of size scale.What should be mentioned that is, also can form more anchor point so that make particulate and/or other chemical substance is attached on the textile substrates surface through other surf zone on the fibrous textile substrates of mechanically roughened processing, thereby make particulate and chemical substance more enduringly attached to the surface of textile substrates.Other mechanical means that textile substrates is carried out roughening also can be implemented within the scope of the invention.Usually, the processing method of any face finishing fiber coefficient of roughness that may be used to obtain to expect, treatment surface zone effectively the dynamics of percentage and/or expectation roll the angle.

Except that using mechanical face finishing technology to make the fiber surface roughening of textile substrates, use for example contains the Chemical composition that of fluorocarbon or the chemical treatment of other anti-fluidity Chemical composition that can be applied on the textile substrates, so that change the non-anti-liquid composition of substrate into anti-liquid composition.If substrate has been anti-liquid, also can not need extra protective agent chemical treatment.And, except the whole microscopic surface texture that forms by face finishing, particulate that can be by adding nano-scale to the textile substrates surface, thereby obtain the roughness of another kind of size scale.Can think that the small particle of these complete waterproof will imitate the nanostructured of the wax crystal on the above-mentioned lotus leaf.Find surprisingly, handle, contain then the component of fluorocarbon and yarn fabric substrate that particulate constituent (preferable particle size is less than 1000 nanometers) is handled presents excellent performance characteristics through mechanical face finishing, comprise that the roughness value (R.F.) (as defined herein) of raising and the dynamics of reduction rolls angle (DRA).

In of the present invention other used, it was useful using crosslinking agent and repellent compound.Repellent compound can comprise the repellent compound that contains fluorocarbon.In one embodiment, can use the waterborne compositions that contains fluorochemical dispersion and crosslinking agent to handle the textile substrates that face finishing is crossed.In another embodiment, can use the waterborne compositions that contains hydrophilic particulate, crosslinking agent and fluorochemical dispersion to handle the textile substrates that face finishing is crossed.Can finish by following various application modes the agent of yarn fabric substrate applied chemistry: include but not limited to, coating, filler, spraying, foam coating, stamp, the suspended substance that exhaustion technology or people can the apply controlled quantity any other technologies to the substrate.Use one or more above-mentioned application technologies can make that chemical constituent is applied on the textile substrates equably.

Chemical treatments can be applied on the textile substrates simultaneously or sequentially.For example, in one embodiment, the mixture (mixing in a bath) that contains protective agent, fine granule and crosslinking agent can be applied on the textile substrates simultaneously by for example filler (padding).After textile substrates applied chemical agent, make treated substrate through drying steps with the liquid of evaporating surplus and the solid active component is retained on the surface of treated substrate.Drying can be finished by normally used any technology in the manufacture process, for example, and any combination of xeothermic, the microwave energy of stenter, infrared heating, steam, superheated steam, pressure heat etc. or above-mentioned technology.In another embodiment, the mixture (containing or do not contain crosslinking agent) that contains particulate constituent is applied to textile substrates, this substrate can be dried or keep hygrometric state, apply a kind of mixture that comprises protective agent and waterproof crosslinking agent then on the surface of particulate constituent, on the surface of textile substrates, carry out chemical treatment in succession.Then, dry this substrate.In another embodiment, the mixture that contains protective agent (containing or do not contain crosslinking agent) is applied on the textile substrates, this substrate can be dried or keep hygrometric state, then, on the surface of the aforementioned protective agent that applies, apply the mixture that comprises protective agent, fine granule and waterproof crosslinking agent again, on the surface of textile substrates, carry out chemical treatment in succession.Then, dry this substrate.

It is desirable to, also can additionally increase a step that the substrate after handling is heated, with the performance and the persistence of further enhancing chemical treatments.This step can be used as curing schedule.(by way of example) as an example, the active component that extra heating can (a) makes a part of chemical treatments is melt-flow together, forms uniform adhesive film cover layer on the surface of substrate; (b) make some fragment in the chemical constituent form optimal arrangement; (c) make between the chemical treatments or chemical treatments and substrate between cross-linking reaction takes place; Or (d) combination of above-mentioned effect.

In many cases, no matter final use, except lasting anti-liquid self-cleaning performance, textile substrates has also realized other performance satisfactorily.These performances include but not limited to, electrostatic protection, crease-resistant, satisfied feel (or sense of touch), color fastness, stink suppress, flammable, dried pollution resistance and similar performance.In these cases, except the front described, can also handle textile substrates with various other chemical finishing agent.For example, it is desirable to handle substrate with the finishing agent that contains following compounds: for example, the combination of antiseptic, antifungal agent, fire retardant, ultraviolet inhibitor, antioxidant, colouring agent, lubricant, antistatic additive, aromatic etc. or above-mentioned chemical agent.Many such chemical treatments can use simultaneously with Chemical composition that of the present invention, and perhaps these are handled also and can use before handling with Chemical composition that of the present invention.Can also after handling, use suitable technology to apply many such chemical treatments with Chemical composition that of the present invention.

In addition, textile substrates can also use typical mechanical finishing technology to handle to obtain outward appearance, intensity, porous and/or the fabric feeling of expectation.For example, it is desirable to textile substrates is carried out following mechanical treatment: for example, the holographic etching of press polish, embossing, etching, iris or holographic etching, film or metal forming, fabric metal coating, thermal finalization, shiinkproof finish, glazing, schreinering, imitative chamois leather sanding, sand washing, emorizing, napping, cropping, repair a mao arrangement, decatizing, form the combination of woven designs or the like or aforesaid way by making water, air or patterned roll.According to using which kind of mechanical treatment,, can obtain some advantages by before or after using machinery of the present invention and/or chemical treatment.For example, except making on the first surface of textile substrates the roughness, the benefit of carrying out press polish at the second surface of textile substrates is can not have a strong impact on the coarse structure that is forming before the chemical treatment on first surface subsequently.In this case, the hydrostatic character of substrate can improve greatly, and can not influence the anti-liquid self-cleaning performance of the height that has formed on the textile substrates first surface.

Within the scope of the invention, it is also contemplated that and to make the symmetrical textile substrates that the surface has dual-functionality.For example, have the textile substrates of first surface and second surface, can be fabricated to and have first water proofing property surface and second hydrophilic surface.Difunctional textile substrates like this can be by the following manner manufacturing: for example, first surface is carried out face finishing to form whole microscopic surface texture, with the two sides of hydrophilic chemical treatments coated substrate, use the first surface of chemical treatments coated substrate of the present invention then.Perhaps, can carry out face finishing to make whole microscopic surface texture, can only apply hydrophilic compounds then second surface to first surface.The method that chemistry is used comprises any aforesaid method, for example, and spraying, foam coating or the like.As a result, the textile substrates of Zhi Zaoing can increase the protection to environment and chemical erosion by repelling the liquid on the substrate first surface in this way, and simultaneously, by the suction of substrate second surface, for example, perspire can increase user's comfort.This shows that if for example this textile substrates is applied on the clothes, these features are obviously satisfactory.

It it should be noted that other trial of only using the water proofing property particulate to make lotus leaf effect surface can not present any repellency to wet component (for example, oil), although can have to a certain degree repellency to glassware for drinking water.But the existing super water proofing property of handling according to the present invention of textile substrates has excellent grease proofness again.In particular, oil droplet (for example, the corn oil droplet) when angle of substrate tilting, can be collected together glomeration and tumble and can not stay oil stain from treated substrate surface.

With reference to Fig. 5, shown fibrous textile substrates 20, it has first side of fiber surface.Represent that 100 microns scale is presented at the bottom near Fig. 5, makes it possible to estimate the approximate size of microscopic surface texture.Fig. 5 is corresponding to the smooth woven polyester textile among the embodiment 10, and it will be described in more detail below.Shown in Fig. 5 A and 5B, fiber surface comprises and extends to lip-deep fiber 23-25 and fiber 30-32.Show that 10 microns scale is presented at the bottom near Fig. 5 A and 5B, makes it possible to estimate the approximate size of microscopic surface texture.Fig. 5 A and 5B have shown the first elevated regions 21a-c and the second sunk area 22a-c, and it is the feature of woven textile substrates.

In this specific embodiment, substrate 20 is woven fabrics, and rough surface is to denude textile substrates by the roller that applies with the fine diamond abrasive grain to make.Woven decorative pattern makes the elevated regions 21a-c that wins be higher than the second sunk area 22a-c.Therefore, in the abrasion processing procedure, the first elevated regions 21a-c receives more roughening, and second sunk area receives less roughening, in fact, also can be subjected to the roughening of this face finishing not at all.This optionally mechanical treatment on textile substrates surface, the some of them zone more likely is subjected to roughening than other zones, is determined by substrat structure usually.For example, substrate is knitting, woven, nonwoven or striped plain weave linen-cotton structure, influence the orientation and the layout of fiber in the textile substrates, thereby handle zone or the fiber (for example, the weft yarn in the woven substrate is to warp thread) that change can be roughened by face finishing.

Insertion frame 21b among Fig. 5 is exaggerated in Fig. 5 A, therefore can see the details of the first elevated regions 21b.And, can see single fiber 23-25 with very big surface roughness, these roughness are the features on imitation lotus leaf surface; That is be to make and keep protection and/or excellent desired feature of preventing the fluidity energy on the textile substrates.Because this rough surface is the integral part on textile substrates surface, these protectives are not easy washing, the abrasion in textile substrates or normally lose in the use.In addition, if use nano level particulate, because its high surface, it is attached to the rough region of these fibers more enduringly.

Insertion frame 22b among Fig. 5 is exaggerated in Fig. 5 B, and it has shown the enlarged drawing of the second sunk area 22b.Just as can be seen, in this zone, roughness on the fiber 30-32 and surperficial irregularity degree are all much smaller in the back.Therefore, this zone is because its geometric position, the surface roughening that the face finishing that is subjected to the present invention hardly and is implemented is handled.The relative percentage that has the area of very big fiber roughness and have an area of obviously less fiber roughness is handled according to employed face finishing and different variation of structure of textile substrates.In fact, it can be such situation: have only following yarn or fiber can demonstrate less surface roughness significantly: these yarns or fiber are hidden and are not subject to processing, because it is positioned at bridge position, for example in woven fabric structure, weft yarn is covered by warp thread physics.

Fig. 5 C and 5D show textile substrates 20 lip-deep nano particles among Fig. 5.Fig. 5 C has shown and has been present in the lip-deep single nanoparticle 41a-41c of rough wearing fiber.Fig. 5 D shows that the part of the nano particle that these are independent can flock together and forms agglomerate 41d on the rough wearing fiber surface.

Fig. 7 A has shown 500 times of stereoscan photographs of the rough wearing fiber of extracting out 41 from embodiment 6 described tent fabric.Rough wearing fiber 41 be by the feature of having used following at least two different sizes form-(a) handle the microscopic surface texture that forms and (b) add extra nano-scale particle on the fiber to by mechanical face finishing.Fig. 7 B has shown the close shot figure of rough wearing fiber 41, and Fig. 7 C, 7D and 7E shown the series of steps that is used for measuring the fiber coefficient of roughness (R.F.), and it will be discussed hereinafter.The top total length of the side profile of measuring determines the approximate or mean roughness of fiber surface in first elevated regions with respect to the lineal measure of frames images, and is indicated in following process.

Fig. 8 A has shown 1000 times of stereoscan photographs of the fiber 50 of pulling out from following embodiment 20 described tent fabric, and the microscopic surface texture that forms on fiber owing to mechanical face finishing has been described.Fig. 8 B has shown the side profile of this image correspondence.Represent that 10 microns scale is presented at the bottom near Fig. 8 A, makes it possible to estimate the approx. dimension of surface characteristics.Those features that the roughness features that forms on this root fiber approaches to present on the lotus leaf.

The protection component

Many compositions can be as the anti-expansion agent composition among the present invention." protective " is normally defined substrate and stops that fluid infiltrates the performance of substrate, for example, and water and/or oil.For example, this substrate can be can block water and oil infiltrate textile substrates in the fiber of textile substrates.

Fluorochemical composition is a kind of useful especially composition.Term " fluorocarbon ", " fluoropolymer " and " fluorochemical " can exchange use here, and each all represents to contain the polymeric material of at least a fluorine-containing fragment.Known many fluorine-containing chemical compositions can both produce protective on textile substrates.

Usually, can be used for fluorochemical protective agent of the present invention comprises and well known in the prior artly can give the fibroid substrate anti-any fluorochemical and the polymer of doing dirty and waterproof, grease proofness.These fluorochemicals and protective polymer agent generally include one or more contain have 3 basic to the perfluor carbochain fluorinated of about 20 carbon atoms, more preferably 6 to 14 carbon atoms.What these fluorine-containing chemical based can have straight chain, side chain or a ring-type fluoridizes allcylene group or its any combination.Fluorine-containing chemical based does not preferably contain the polymerizable unsaturated olefin, but randomly contains outstanding (catenary) hetero atom, for example, and the sulphur of oxygen, divalence or sexavalence or nitrogen.Preferred fully-fluorinated group,, also can there be hydrogen or chlorine replacing group, although an atom only occurs on preferred per two carbon atoms.In addition, preferred any fluorine-containing chemical based contains about 40 to about 80wt% fluorine, more preferably contains about 50 to about 78wt% fluorine.The preferred perfluorinate of the end portion of group preferably contains at least 7 fluorine atoms, for example, and CF ₃CF ₂CF ₂-, (CF ₃) ₂CF--, SF ₅CF ₂--.Perfluor fat-based (that is molecular formula C, _nF _2n+1--) be most preferred fluorine-containing chemical based embodiment.

The representational fluorochemical protective agent that can be used for the present invention's processing comprises fluorochemical carbamate, urea, ester, ether, alcohol, epoxides, allophanate, acid amides, amine (and salt), acid (and salt), carbon imidodicarbonic diamide, Gua, oxazolidone (oxazolidinone), isocyanurate and biuret.The admixture of these compounds also can be considered to use.The representational fluorochemical polymer that can be used for the present invention's processing comprises the fluorochemical acrylate monomer, with the Voncoat R 3310 that replaces or contain and do not contain the copolymer of fluorochemical acrylate monomer of the monomer copolymerization of non-ethene fluorine, the monomer that does not wherein contain non-ethene fluorine is methyl methacrylate for example, butyl acrylate, the acrylate of oxyalkylene and the how pure oligomer of polyoxyalkylene and methacrylate are (for example, the oxyethylene glycol dimethylacrylate, the polyoxyethylene glycol dimethylacrylate, acrylic acid methoxyethoxy ester and polyoxyethylene glycol acrylate), glycidyl methacrylate, ethene, butadiene, styrene, isoprene, chlorobutadiene, vinylacetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylonitrile, vinyl chloroacetate, vinylpyridine, vinyl alkyl ether, vinyl alkyl ketone, acrylic acid, methacrylic acid, acrylic acid 2-hydroxyl ethyl ester, N hydroxymethyl acrylamide, 2-(N, N, the N-trimethyl) ethyl-methyl ammonium acrylate (2-(N, N, N-trimethylammonium) ethyl methacrylate), and 2-acrylamido-2-methyl propane sulfonic acid (AMPS).The performance that the relative quantity of the employed various comonomers that do not contain non-ethene fluorine obtains according to handled textile substrates, expectation usually and be applied to the mode on the textile substrates and select empirically.Available fluorochemical finish also comprises the admixture of above-mentioned various fluorochemical protective polymer agent, also comprises the admixture of aforementioned fluorochemical and these protective polymer agent.

The commercially available fluorochemical protective agent that can be used in combination with the present invention includes but not limited to the Scotchgard of 3M company ^TMThe Zonyl of series fluorochemical protective agent, E.I.Du Pont Company ^TMThe Repearl of series fluorochemical protective agent, Mitsubishi international corporation ^TMSeries fluorochemical protective agent.Useful especially in the present invention is Mitsubishi company

F-8025 or Repearl F-7000.Other fluorochemical, for example, the Unidyne that Daikin U.S. Co., Ltd produces ^TMPerhaps the product of OMNOVA Solutions company production also can use.

Except fluorochemical, other chemical protector, for example, polysiloxanes protective agent, wax or the like also can use in the present invention to obtain barrier propterty.The polysiloxanes protective agent can have been bought from GE chemical company, Dow Corning company, Kelmar industrial group and other company.The example of commercially available polysiloxanes protective agent comprises the SE-40A that the Kelmar industrial group in Dow Corning 346 Emulsion that the Dow Corning company in available city sells and South Carolina Duncan city sells.Wax can have been bought from Petrolite company, Allied chemical company, Cabot Consos company and other companies.An example of commercially available wax protective agent is Consopel ZW, the zirconium cerul emulsion that the Consos Co., Ltd in North Carolina state Xia Luote city sells.

Particulate constituent

Various microparticle materials (inorganic or organic) also can use in the present invention jointly.Preferred particulate comprises at least a material that is selected from silicate, doped silicate, mineral, silica, polymer, carbon, graphite, slaine, metal dust, silica coating metal powder, inorganic oxide (for example metal oxide) etc. or its combination.

In particular, the example of operable particulate including, but not limited to, silica, cataloid, aluminium oxide, zirconia, titanium oxide, zinc oxide, winnofil, polytetrafluoroethylene (PTFE), full fluorine copolymer, with the copolymer of tetrafluoroethene, polyvinylpyrrolidone (PVP) or the like.These particles can also be by surface modification, for example, and grafting.

Select the size of particle should consider Several Factors.Particle diameter is too little can not to provide proper surface roughness so that trap (trap) air or may need the height of follow-up agglomerate to fill the roughness features that could obtain satisfaction among the present invention on the surface of substrate.Particle is too greatly for the dyed textiles substrate, the white phenomenon of frost can occur, or is worn away easily in the use of textile substrates and operational maintenance.Usually, think that particle diameter can provide good effect for 1 nanometer to about 50 microns in various application of the present invention.Particle diameter be about 5 nanometers to about 1 micron be useful especially, particle diameter is that effect is fine in some applications between about 50 nanometers for about 10 nanometers.Use the particulate of these sizes can build nano level roughness, be similar to the wax shape crystal on the lotus leaf, increasing the mechanically roughened fiber roughness of being given by face finishing, the mechanically roughened formation size of face finishing is usually less than 100 microns microscopic surface texture.

Just as used herein, on behalf of a big class, term " inorganic oxide " or " metal oxide " contain the material of the metal cation that at least a and oxygen anion or hydroxy anion or oxygen combine with the mixture of hydroxyl ion.This material also comprises the water of bonding or adsorption form, and can comprise a spot ofly, for example, is less than the counter ion counterionsl gegenions of 5 weight %, for example, and sodium ion, carboxylic acid ion, chlorion, nitrate ion or the like.For purpose of the present invention, expectation is that metal oxide or inorganic oxide are in very thin released state usually.It is a kind of to the useful especially form of the present invention that colloidal dispersion provides.

Below be according to application-specific employed component in reality of the present invention:

Nalco 1042 ^TMThe colloid acidic silicasol cationic aqueous solution of cataloid-34wt% solid, (" Nalco ") is commercially available in Nalco chemical company, Nei Puweier city, Illinois;

Nalco 1050 ^TMThe colloid acidic silicasol cationic aqueous solution of cataloid-50wt% solid, Nalco is commercially available; Colloidal sol pH value is 9, and average grain diameter is diameter 20 nanometers;

Nalco 2326 ^TMThe colloid acidic silicasol cationic aqueous solution of cataloid-15wt% solid, Nalco is commercially available; Colloidal sol pH value is 9, and average grain diameter is diameter 5 nanometers;

Nalco 2327 ^TMThe colloid acidic silicasol cationic aqueous solution of cataloid-40wt% solid, Nalco is commercially available; Colloidal sol pH value is 9, and average grain diameter is diameter 20 nanometers;

Nalco 2329 ^TMThe colloid acidic silicasol cationic aqueous solution of cataloid-40wt% solid, Nalco is commercially available; Colloidal sol pH value is 9, and average grain diameter is diameter 75 nanometers;

Nalco 1056 ^TMThe aqueous colloid suspension of the aluminized silica particle of aluminized silica-30wt% solid (26% silica and 4% aluminium oxide), Nalco is commercially available;

Nalco 88SN-126 ^TMThe titanium dioxide water-dispersion liquid of colloidal titania-10wt% solid, Nalco is commercially available;

Nalco 88SN-123 ^TMThe tin oxide aqueous dispersions of colloid tin oxide-22wt% solid, Nalco is commercially available;

Cab-O-Sperse S3295 ^TMThe aerosil aqueous dispersions of aerosil-15wt% solid, the Cabot company in Pennsylvania Boyertown city is commercially available; The pH value of dispersion liquid is 9.5, and the particle diameter of the primary particle of average cohesion is about 100 nanometers of diameter;

Cab-O-Sperse A205 ^TMSilica, Cabot company is commercially available;

Ludox AS 40 ^TMThe colloidal silica sol aqueous solution of cataloid-40wt% solid, the Grace Davison company in Colombia city, the Maryland State is commercially available; Colloidal sol pH value is 9, and average grain diameter is diameter 22 nanometers;

Ludox AM ^TMThe colloidal silica sol aqueous solution of cataloid-30wt% solid, Grace Davison company is commercially available; Colloidal sol pH value is 9, and average grain diameter is diameter 12 nanometers;

Ludox CL-P ^TMThe colloid aqueous solution of the silica of colloidal alumina coating-40wt% solid, Grace Davison company is commercially available; Colloidal sol pH value is 4, and average grain diameter is diameter 22 nanometers;

Ludox TMA ^TMThe colloidal silica sol aqueous solution of cataloid-34wt% solid, Grace Davison company is commercially available; Colloidal sol pH value is 4.7, and average grain diameter is diameter 22 nanometers;

Sipernat 22LS ^TMHydrophily precipitated silica-dried powder, German Degussa company is commercially available; Average grain diameter is diameter 4.5 nanometers; With

Viviprint 540 ^TMThe crospovidone particle, the solid of 10wt% obtains from ISPTechnologies company.

In some cases, also can use to have other functional particle.These particles can provide the extra performance that exceeds structure building feature as described herein.For example,

Particle from the Mei Liken chemical company of South Carolina Spartanburg, can provide the antibiotic property feature for textile substrates.Zinc oxide particles can provide the performance of inhaling stink.Zelec ^TMParticle can provide anlistatig performance equally from Mei Liken chemical company.Firebrake ZB particle or antimony pentoxide can provide fire-retardant and mycocidal performance.The iron-based particulate can provide magnetic and microwave absorbing property.

Linked

Can randomly use linked among the present invention, comprise water-fast substantially linked (for example, waterproof).In other prescriptions, the Qinshui crosslinking agent can use.

In other embodiments, the water proofing property linked can comprise isocyanate derivates (protected derivatives of isocyanates) etc. or its combination of protection.The vulcabond of protection can be suitable linked.The monomer or the polymer that contain (blocked) isocyanate compound of two or more sealings can be most preferred linked.An available linked is

MF ^TM, can obtain from Mitsubishi company.Comprising of other

DAN (a kind of polyurethane) can derive from Clariant company; And

XANTM derives from E.I.Du Pont Company.

Another kind of available crosslinking agent is Milligard MRX ^TM, a kind of polyurethane-base crosslinking agent can derive from the Mei Liken chemical company in Spartanbury city, the South Carolina.

The method of testing explanation

A) waterproofing tests

Water proofing property is to test according to 3M waterproofing tests II (in May, 1992).Classification standard is 0-10, " 0 " expression waterproof degree the poorest (substrate has higher surface energy), and " 10 " expression waterproof degree best (substrate has lower surface energy), and 3M waterproofing tests grade is as follows:

The 0th, 0wt% isopropyl alcohol (IPA), 100wt% water

The 1st, 10wt% isopropyl alcohol (IPA), 90wt% water

The 2nd, 20wt% isopropyl alcohol (IPA), 80wt% water

The 3rd, 30wt% isopropyl alcohol (IPA), 70wt% water

The 4th, 40wt% isopropyl alcohol (IPA), 60wt% water

The 5th, 50wt% isopropyl alcohol (IPA), 50wt% water

The 6th, 60wt% isopropyl alcohol (IPA), 40wt% water

The 7th, 70wt% isopropyl alcohol (IPA), 30wt% water

The 8th, 80wt% isopropyl alcohol (IPA), 20wt% water

The 9th, 90wt% isopropyl alcohol (IPA), 10wt% water

The 10th, 100wt% isopropyl alcohol (IPA)

Specimen is placed on the smooth horizontal surface.3 droplet test liquids, about 5 millimeters of diameter is placed on 3 zoness of different of specimen lightly with dropper or pipette.The drop interference-free left standstill for 10 seconds.If after 10 seconds, two in 3 are still spherical as can be seen to hemisphericals, and then sample is by test.The number of degrees of sample should be still to keep the maximum test liquid of the visible numbering of drop.

B) grease proofness test

Grease proofing test is carried out according to AATCC method of testing 118-2000.Classification standard is 0-8, " 0 " expression grease proofness the poorest (substrate has higher surface energy), " 8 " expression grease proofness best (substrate has lower surface energy).Grease proofing grade is divided into:

The 0th, Nujol ^TMMineral oil (substrate is moistened by oil immersion)

The 1st, Nujol ^TMMineral oil

2 is Nujol/ hexadecanes (by volume calculating) of 65/35

The 3rd, hexadecane

The 4th, n-tetradecane

The 5th, n-dodecane

The 6th, n-decane

The 7th, normal octane

The 8th, normal heptane

Specimen is placed on the smooth horizontal surface.From numbering minimum test liquid, diameter is approximately a droplet test liquid of 5 millimeters is placed on specimen lightly with dropper or pipette several zoness of different.The drop interference-free left standstill for 30 seconds, and observed drop at miter angle.If after 30 seconds, on the interface of liquid-substrate, sample substrate do not have wetting or the infiltration and do not have wicking occur in drop around, then sample by the test.The grease proofing grade of sample is the test liquid that does not have the numbering maximum of wetting substrate in 30 seconds.

C) spray process grading test

Spray process grading test is carried out according to AATCC (American Association of TextileChemists and Colorists (U.S. textile chemist and tinter association)) method of testing 22-2000.Spray degree grade is divided into:

The 100-upper surface does not have adhesion and wetting

The 90-upper surface is adhesion or wetting at random slightly

The 80-upper surface is wetting at the spray point

70-entire upper surface part is wetting

The 50-entire upper surface is all wetting

0-entire upper surface and lower surface are all wetting

D) dynamics is rolled angle (DRA) test

Use traditional contact angle measuring method to be difficult to relatively resemble the barrier propterty that has high water-proof surface among the present invention like this, because be difficult to measure reliably high contact angle (＞150 degree).Difficulty on textile substrates even more is because the structure of textile substrates causes determining baseline well.Using water droplet dynamics to roll angular measurement tries to replace.Here, dynamics is rolled the angle and is defined as when water droplet drips in advance on the surface that tilts, and water droplet will roll thereon by the minimum angles on the surface of preset distance.Less dynamics is rolled the higher protective of angle numeric representation.

Dynamics is rolled the angle and is measured by following steps.

6 * 4 inches sample setup are on test desk, and the angle of test desk can be adjusted in 0 to 90 degree scope with respect to horizontal direction.Sample is level and smooth corrugationless under the tension force of appropriateness.Then, blow sample with the air ionizer at test desk top, so that any electrostatic charge that may exist on the dispersing surface.Use syringe needle with the deionized water drop of predetermined quality (be generally 11 hospitable) to 12 from distance from 1 centimetre of sample surfaces, across the width of sample, drop onto on the sample that tilts in advance.Adjust the angle of inclination gradually, write down the minimum angles that at least 5 water droplets roll across preset distance.Preset distance is generally 3 centimetres.

E) home washings program

The home washings program that is used for testing washability is carried out according to AATCC method of testing 130-2000, use washing procedure 1 (105F ° of washing) and

Instant cleanser.

After " washability " was generally defined as standard wash circulation by reasonable number of times, substrate remained on the function of expectation the ability of acceptable degree.Substrate can be a textile substrates, for example, and fabric.

F) the wear-resisting test of Martindale

The wear-resisting test of Martindale is carried out according to revised ASTM D4966-98, uses Mark III abrasion test instrument BS 5690 (Shirley Development Co., Ltds).7 * 7 inches sample is placed on the testboard.Use is placed on woven wool fabric in abrasion cylinder (not having extra weight) as abrasive material.This fabric is a plain weave hybridization worsted wool fabric, and weight is 5.8 ounce per square yard, derives from the TexFabric Co., Ltd of Pennsylvania Xipi Ci Dun city (West Pittston).Fabric is formed by R63Tex/2 warp thread and R74Tex/2 weft yarn plain woven, through close 43 pieces/inch, and 30 pieces/inch of filling densities.Warp thread is that 27.5 microns wool fiber is made in single 540TPM z twists with the fingers by diameter, and weft yarn is that 29 microns wool fiber is made in single 500TPM z twists with the fingers by diameter.

Then, sample is subjected to the abrasion circulation of predetermined quantity.

The specific embodiment

A) mechanically roughened processing

With face finishing technology to textile substrates (for example woven, knitting or adhesive-bonded fabric, striped scrim) roughening.This comprises that the abrasion roller (perhaps some uses sand paper) with the coated with CVD (chemical vapor deposition) diamond of a series of particular size or various granularity combinations carries out slight roughening to the surface of substrate.Can see that any machinery of sand milling of being used for suitable particle size well known in the prior art can be used for handling.In addition, in order to increase treatment effect, be expected at face finishing handle before or among can use chemical sweller.Can carry out face finishing technology on low-level unconventional, can not produce a large amount of broken fibers on the textile substrates surface so that make at least a portion surface roughening.Also can make otherwise roughening is carried out on the textile substrates surface, for example, particulate sandblast, laser ablation, plasma treatment and chemical etching (for example using acid).Therefore, chemical method, mechanical means or other method or it is in conjunction with all can be used for roughening is carried out on the surface of textile substrates arbitrarily.

In the listed embodiment of this paper, according to the following steps substrate is carried out preliminary treatment.

A fabric is cut into about 13 * 60 inches size.Two ends of fabric are sewn to and form a ring together.Fabric is placed on the proprietary homemade abrader then, fabric loop is placed on the abrasion roller.The tension force of fabric is by the control of inflation cylinder.Fabric is with the speed operation of 8 yards of per minutes.Be Balance Treatment, on both direction, use the circular treatment fabric of equal number usually.The tension force of the fabric that the rank of handling depends on the granularity of treatment tube (g), determined by the pressure of cylinder (p) and be applied to period (n) on the fabric.Handle rank and be expressed as g-p-n.For example, 1200-30-12 represents, handling 12 circulations under with the pressure of abrasion roller at 30psi of 1200 granularities on each direction.In general, the granularity of use about 600 to about 1200 is very suitable among the present invention.Typically, has only the part fabric face by face finishing technology roughening.The percentage that the area of roughening accounts for total surface area is determined by fabric construction, also can estimate from representational stereoscan photograph.Evaluation method is following to be described in detail.Because the present invention uses fine granularity abrasion roller, so the quantity of broken fiber is far fewer than the traditional face finishing technology with coarseness abrasion roller in the unit are that is caused by face finishing technology.

B) be used for measuring the method that rough surface amasss percentage

Describe the shooting of all electromicroscopic photographs in detail and be used for measuring surface roughness and the sample preparation of the calculating coefficient of roughness in following part.Treated fabric is placed in the SEM, so that see surperficial distinct image, the placement of position wants to make the surface roughness that is formed by outstanding, scraped finish, particle etc. to be clearly seen.Digital picture is long * 600 pixel height of 800 pixels.The fabric face image amplifies 50 times of shootings.Image saves as 8bit RGB file with the jpeg form.For example, Fig. 5 shows the original image of the fabric Q of the embodiment 10 that is obtained by SEM.For the fabric face percentage that focuses on roughening (that is, shown in regional 21b), can extract the image that a part only focuses on treated textile surface, shown in Fig. 9 A.In this case, treated textile substrates surface is corresponding to being subjected to the first elevated regions 21b that face finishing is handled and had tangible surface roughness.These regional 21b, as hereinafter institute's description in more detail, its coefficient of roughness is more than or equal to 1.10 usually.The actual size of sample shown in Fig. 9 A is that 2.4 mm wides * 1.48 are millimeter high.This is the minimum area in the required scope of this analysis.

For analyzing, use two software kits: Adobe Photoshop6.0.1, the Adobe Systems Incorporated company in San Jose city, California provides; And Image ProPlus 4.5, the Media Cybernetics company in Silver Spring city, the Maryland State provides.The image that extracts converts the grey scale image (every pixel occupies a gray value, from 0 to 255, or from black to white) of 8 bytes in Image Pro Plus 4.5.Then, extraction document is transformed into Adobe Photoshop.Be the pixel of the figure on the surface (being similar to the zone of 21b) of isolating expression substrate roughening the substrate surface (being similar to the zone of 22b) that does not have roughening from expression, use the erase tool of 3-pixel diameter to mark those pixels of the surface fiber of roughening in the image.In order to realize this purpose, eraser is configured to change all the interior pixels of zone that stride across, and simultaneously these pixels is activated to black, and pixel value is 0.Handle enlarged image (on the interface of Adobe Photoshop, amplifying 200% or bigger) with mouse, in 50 times electromicroscopic photograph, can see the surface roughening given by technology (the fiber roughening also remains in the plane that is parallel to substrate surface substantially) clearly, sketch the contours of those parts in the electromicroscopic photograph exactly with hand, and to set those pixels be 0.Fig. 9 B has shown the image the same with Fig. 9 A, still, sets the part of substrate roughening for black (pixel value is 0) with said method.This image in Image Pro Plus, be saved into tiff file as with post analysis.

Use Image Pro Plus, the image file that the pixel of representing roughened surface is set to black (pixel value is 0) is opened.This image is used to calculate the long-pending percentage of roughened surface.In principle, represent percentage that the black picture element of surface roughening area compares with the sum of all pixels of surface image percentage (PS) as treated surface area.In order to measure PS, Image ProPlus allows the user to select this part according to the pixel value and the size of some part of image.Because the pixel of expression roughened surface has been set black (pixel value is 0) for, approach 0 pixel by being partitioned into (selection), can from image, select background.Some complexity.Because, in an image, may have shade, there is the pixel value of some pixel objects to approach zero but presentation surface roughening part not.These pixel objects always comprise the littler pixel of specific surface roughening part.Therefore, be denoted as the background of Pixel Dimensions greater than shade size in the image by requiring the pixel object, the analyst gets rid of shade (this changes according to image) from profile.For the purpose of complete, what need indicate is, the calculating of roughened surface object pixel will make any pixel " hole " in the overall background of selected pixel all be selected automatically, and any pixel should be contiguous mutually in 4 join domains, is denoted as background parts.This means, the object in the image should by have on the specific pixel of being located immediately at, under or the neighbours on arbitrary limit be connected to main body in the image; Only the pixel that connects by the diagonal angle will not be included in the selected background object.Fig. 9 C is the example of the surface roughness image that sketches the contours for Fig. 9 B.In this case, the pixel (all are similar to the zone of 21b) of the surface portion of expression roughening is set to 255 looks (i.e. white), and the pixel value of other parts is set to 0 (being black).Image is converted into the binary picture that has only the black and white pixel.

The task of handling image among Fig. 9 C is measured the quantity and the image total pixel number of white (coarse) pixel exactly.Use the partition tools among the Image Pro Plus, the same with all pixels with 255 (whites), can calculate the pixel count (X that represents coarse part in this example _R).Can obtain image total pixel number (X with the bitmap among the ImagePro Plus _T) or do not calculate with there being to set the partition tools of cutting apart grade once more.Can calculate coarse percentage of surface area PS now:

PS＝X _R/X _T

C) chemical application process

The embodiment of the textile substrates that all provide below using handles according to one of following method, and is indicated by corresponding.

I) one-step method:

1. an about fabric of 13 * 17 inches is immersed in the bath that contains the Chemical composition that comprises desirable chemical reagent.

2. except as otherwise noted, used chemical percentage (%) all is based on the percentage by weight of the gross weight of prepared bath, and when the chemical percentage of chemicals or gram number are given, surplus is a water.In addition, chemical percentage is based on the chemicals that obtains from manufacturer, and like this, if said composition contains 30% active component, the X% of this 30% composition is used so.

3. after this fabric is completely soaked, fabric is removed bathing from handling, and is process between the mangle roller of 40psi from pressure, obtains about 30 to about 100% uniform pick-up rate.

4. fabric is tensioned and is fixed on the stenter to keep ideal dimensions.

5. pin stenter is placed in the Despatch stove, and temperature is about 350 to 380F °, dry about 5 to about 10 minutes, solidifies arrangement then.

6. in case take out from stove, fabric is taken off from pin stenter and balance at room temperature before test.

II) two-step method:

1. repetition one-step method except that all chemicals being added in the chemical bath, will contain one or more chemical agents of Chemical composition that, be applied on the fabric respectively according to following particular order.

2. fabric is dipped into and comprises in one or more chemical agents that comprise Chemical composition that baths.

This fabric by complete wetting after, fabric is removed from handle to bathe, pass through between the mangle roller of in one-step method, describing.

4. fabric is following dry about 5 minutes at about 300 to 350F ° in the Despatch stove.

5. then, fabric is dipped in the second fresh bath that contains the desirable chemical agent that comprises second Chemical composition that.

6. the curing that is dried as described in fabric such as the one-step method then.

III) spray process:

1. about fabric of 13 * 17 inches is tensioned and is fixed on the stenter.

2. use at the spray gun Model 150 of 20psi pressure operation (Badger Air-Brush company), then, with comprising that the Chemical composition that of desirable chemical agent sprays this fabric.Carry out the spray operation and do not had drippage by complete wetting up to fabric face.

3. pin stenter is placed in the Despatch stove, and temperature is about 200 to 350F °, dry about 5 to about 10 minutes, solidifies arrangement.

4. in case take out from stove, fabric is taken off from pin stenter and balance at room temperature before test.

Various embodiment of the present invention embodies by following examples, but specific embodiment provided here does not limit scope of the present invention.

Embodiment 1

Little danier twills

Face finishing

One-step method is handled

The bath that contains following chemicals of preparation 200 grams:

1.2 the Sipernat 22LS of gram (or 1%) ^TM, the hydrophily silica dioxide granule derives from German Degussa company.

2.8 the Repearl F-7000 of gram (or 4%) fluoridizes anti-fouling agent, derives from Mitsubishi company.

3.2 the Milligard MRX of gram (or 1%) ^TM, crosslinking agent derives from Mei Liken chemical company.

With little danier (microdenier) polyester textile of this Chemical composition that according to aforementioned one-step method processing 100%.The wet pickup of Chemical composition that is about 50% on this fabric.

Little Denier polyester fabric is that the Milliken Co. from South Carolina Spartanburg city obtains.Fabric is woven together by modified continuous filament polyester 1/140/200 danier warp thread and modified continuous filament polyester 1/150/100 danier weft yarn, 2 * 2 twill left to rights, 175 warp thread of fabric per inch, 80 weft yarns (below refer in particular to be used for " little danier twills " of the present invention).With the rank of coated with CVD (chemical vapor deposition) diamond roller, make the fabric roughening with face finishing technology with 1200-30-32.About 19% surface area is subjected to the roughening of face finishing technology.

Fabric after the processing is measured water and oil-resistant, spray degree, dynamics with preceding method and is rolled the angle, as former state (" AR ").The result is shown in 1A.Measure the spray degree after the home washings 1 time, 5 times, 10 times and 20 times and dynamics is rolled the angle.The result is shown in 1B.Spray degree and dynamics are rolled the angle and also can be measured after Martindale denude 1000 circulations, 2000 circulations, 5000 circulations, 10000 circulations and 20000 circulations.The result is shown in 1C.

Embodiment 2

Little danier twills

Face finishing

Two-step method is handled

The little danier twills of polyester of the surface dressing as described in example 1 above of the face finishing of use same levels are handled with aforementioned two-step method.In the first step of this method, on this fabric, use 2% Ludox AM, average grain diameter is the colloidal silica particles of 12 nanometers, Grace Davison company is commercially available, and is dry then.In second step, subsequently with 4.0% Repearl F-7000 and 1% Milligard MRX ^TMMixture be applied on the fabric.

Fabric after the processing is measured water and oil-resistant, spray degree, dynamics with preceding method and is rolled the angle, as former state (" AR ").The result lists 1A in.Measure the spray degree after the home washings 1 time, 5 times, 10 times and 20 times and dynamics is rolled the angle.The result lists 1B in.Spray degree and dynamics are rolled the angle and also can be measured after Martindale denude 1000 circulations, 2000 circulations, 5000 circulations, 10000 circulations and 20000 circulations.The result lists 1C in.

Comparative example 3

Little danier twills

No particle and the arrangement of no matte

Except Sipernat 22LS ^TMComposition repeats embodiment 1 outside being removed from bathe.Little danier twills are without face finishing technology roughening.

Fabric after the processing is measured water and oil-resistant, spray degree, dynamics with preceding method and is rolled the angle, as former state (" AR ").The result lists 1A in.

Embodiment 4

The automobile twills

Face finishing

One-step method is handled

Except little danier twills are substituted by automobile inside pool polyester textile, repeat embodiment 1.The wet pickup of Chemical composition that on this fabric about 98%.

This automobile inside pool polyester textile derives from the Milliken Co. in Spartanburg city, the South Carolina.Fabric is woven together by modified continuous filament polyester 2/150/34 danier warp thread and weft yarn, 2 * 2 twill left to rights (below refer in particular to be used for " automobile twills " of the present invention).Fabric is dyed filbert.With the roller of coated with CVD (chemical vapor deposition) diamond with rank 1200-30-24, with this fabric of face finishing technology roughening.About 20% surface area is subjected to the roughening of face finishing technology.

Comparative example 5

The automobile twills

No particle and the arrangement of no matte

Except Sipernat 22LS ^TMComposition repeats embodiment 4 outside being removed from bathe.This fabric is without face finishing technology roughening.

Embodiment 6

The polyester tent fabric

Face finishing

One-step method is handled

Except little danier twills are substituted by the polyester tent fabric, repeat embodiment 1.The wet pickup of Chemical composition that on this fabric about 88%.

This polyester tent fabric derives from the Milliken Co. in Spartanburg city, the South Carolina.Fabric is a plain cloth, and warp-wise and broadwise have 70 daniers, 36 threads distortion PET yarn.The per inch fabric is made of about 90 warp thread and 80 weft yarns.(below refer in particular to be used for " tent fabric " of the present invention).Fabric is dyed filbert.With the roller of coated with CVD (chemical vapor deposition) diamond with rank 600-30-12, with this fabric of face finishing technology roughening.About 17% surface area is subjected to the roughening of face finishing technology.

Fabric after the processing is measured water and oil-resistant, spray degree, dynamics with preceding method and is rolled the angle, as former state (" AR ").The result lists 1A in.Spray degree and dynamics are rolled the angle and also can be measured after Martindale denude 1000 circulations, 2000 circulations, 5000 circulations, 10000 circulations and 20000 circulations.The result lists 1C in.

Comparative example 7

Tent fabric

No particle and the arrangement of no matte

Except Sipernat 22LS ^TMComposition repeats embodiment 6 outside being removed from bathe.This fabric is without face finishing technology roughening.

Embodiment 8

Polyester ship cover fabric

Face finishing

One-step method is handled

Preparation 200 grams contain the bath of following chemicals:

1.2 the Sipernat 22LS of gram (or 1%) ^TM, the hydrophily silica dioxide granule derives from Degussa company.

2.10 the Repearl F-7000 of gram (or 5%) fluoridizes anti-fouling agent, derives from Mitsubishi company.

3.2.4 the Milligard MRX of gram (or 1.2%) ^TM, crosslinking agent derives from Mei Liken chemical company.

Handle 100% polyester ship cover fabric with this Chemical composition that according to aforementioned one-step method.The wet pickup of Chemical composition that on this fabric about 66%.

This polyester ship cover fabric derives from the Milliken Co. in Spartanburg city, the South Carolina.Fabric is woven in a plain weave structure by modified continuous filament polyester 4/150/36 danier warp thread and modified continuous filament polyester 4/150/36 danier weft yarn, 54 warp thread of per inch, 36 weft yarns (below refer in particular to be used for " polyester ship cover fabric " of the present invention).With the roller of the coated with CVD (chemical vapor deposition) diamond of 600 granularities and 1200 granularity combinations with rank 1200-30-24, with this fabric of face finishing technology roughening.About 25% surface area is subjected to the roughening of face finishing technology.

Comparative example 8

Ship cover fabric

No particle and the arrangement of no matte

Except Sipernat 22LS ^TMComposition repeats embodiment 8 outside being removed from bathe.This fabric is without face finishing technology roughening.

Embodiment 10

Flat woven polyester textile (fabric Q)

Face finishing

One-step method is handled

Except ship cover fabric is substituted by flat woven polyester textile, repeat embodiment 8.The wet pickup of Chemical composition that on this fabric about 32%.

This flat woven polyester textile derives from the Milliken Co. in Spartanburg city, the South Carolina.This fabric is 1 * 1 plain weave, and through upwards there being 34,4.45 daniers/root PE yarn have 34 on the broadwise, 4.19 daniers/root PE yarn (below refer in particular to be used for " fabric Q " of the present invention).With this fabric of face finishing technology roughening, earlier with the roller of the coated with CVD (chemical vapor deposition) diamond of 600 granularities and 1200 granularity combinations with rank 600-30-6, follow with rank 1200-30-16, fabric is carried out roughening.About 18% surface area is subjected to the roughening of face finishing technology.

Comparative example 11

Flat woven polyester textile (fabric Q)

No particle and the arrangement of no matte

Except ship cover fabric is substituted by fabric Q, repeat embodiment 9.This fabric is without face finishing technology roughening, Sipernat 22LS ^TMComposition is removed from bathe.

Comparative example 12

Little danier twills

No matte arrangement

U.S. Patent application No.2002/0016433 A1 preparation according to people such as Keller

Preparation is according to the Chemical composition that of the embodiment 9 of the U.S. Patent application No.2002/0016433 A1 of Harald Keller etc.

According to aforementioned spray process, use this Chemical composition that to handle the little danier twills of polyester.This fabric is without face finishing technology roughening.

Fabric after the processing is measured water and oil-resistant, spray degree, dynamics with preceding method and is rolled the angle, as former state (" AR ").The result lists table 1A in.Fabric after the processing is also measured wash resistant and anti-wear performance, and the result lists table 1B and 1C respectively in.

Comparative example 13

The automobile twills

No matte arrangement

Except little danier twills are substituted with twills by automobile, repeat comparative example 12.This fabric is without face finishing technology roughening.

Comparative example 14

Tent fabric

No matte arrangement

Except little danier twills are substituted by tent fabric, repeat comparative example 12.This fabric is without face finishing technology roughening.

Comparative example 15

Ship cover fabric

No matte arrangement

Except little danier twills are substituted by ship cover fabric, repeat comparative example 12.This fabric is without face finishing technology roughening.

Comparative example 16

Flat woven polyester textile (fabric Q)

No matte arrangement

Except little danier twills are substituted by fabric Q, repeat comparative example 12.This fabric is without face finishing technology roughening.

Embodiment 17

Ship cover fabric

Face finishing

One-step method is handled

Preparation 200 grams contain the bath of following chemicals:

1.10 the Repearl F-7000 of gram (or 5%) fluoridizes anti-fouling agent, derives from Mitsubishi company.

2.5 the LUDOX CL-P colloidal alumina coating silica dioxide granule of gram (or 2.5%) derives from Grace Davison company.

3.8 the Milligard MRX of gram (or 4%) ^TM, crosslinking agent derives from Mei Liken chemical company.

With this Chemical composition that according to the polyester ship cover fabric (with the rank of 600-30-12, use the rank of 1200-30-24 then, carry out roughening) in the aforementioned one-step method Processing Example 8 with face finishing technology.The wet pickup of Chemical composition that on this fabric about 65%.Fabric after the processing is measured water and oil-resistant, spray degree, dynamics with preceding method and is rolled the angle, as former state (" AR ").The result lists table 1A in.Fabric after the processing is also measured wash resistant and anti-wear performance, and the result lists table 1B and 1C respectively in.

Embodiment 18

Ship cover fabric

No matte arrangement

One-step method is handled

The ship cover fabric that is not had face finishing technology roughening to cross except the ship cover fabric of surface dressing substitutes, repeat embodiment 17.

Embodiment 19

Ship cover fabric

Face finishing

One-step method is handled

Preparation 200 grams contain the bath of following chemicals:

2.2 the Viviprint 540 of gram (or 1%), the polyvinylpyrrolidone particle derives from ISPTechnologies company.

3.1.6 the LUDOX CL-P of gram (or 0.8%), colloidal alumina coating silica dioxide granule derives from Grace Davison company.

4.2.4 gram (or 1.2%) Milligard MRX ^TM, crosslinking agent derives from Mei Liken chemical company.

With this chemistry fabric according to the polyester ship cover fabric in the aforementioned one-step method Processing Example 8 (use face finishing technology, earlier use the 600-30-12 rank, then use the 1200-30-24 rank).The wet pickup of chemistry fabric on this fabric about 68%.

Embodiment 20

The polyester tent fabric

Face finishing

No particle

One-step method is handled

With the polyester tent fabric in the aforementioned one-step method Processing Example 6 (using face finishing technology, the 600-30-12 level).1.0% Repearl F-7000 and 2%Milligard MRX ^TMMixture be applied on the fabric.

Comparative example 21

Tent fabric

No particle and the arrangement of no matte

With the polyester tent fabric in the aforementioned one-step method Processing Example 6 (no matte finishing technique).1.0% Repearl F-7000 and the mixture of 0.25%Milligard MRXTM are applied on the fabric.

Fabric after the processing is measured water and oil-resistant, spray degree, dynamics with preceding method and is rolled the angle, as former state (" AR ").The result lists table 1A in.

Embodiment 22

Nylon/cotton blended fabric

Face finishing

Two-step method

Handle the blend fabric of 50% nylon/50% cotton with aforementioned two-step method.In the first step of this method, 2% Ludox AM ^TMColloidal silica particles, average grain diameter is 12 nanometers, derives from Grace Davison company, is applied on this fabric, then carries out drying.In second step, 5.0% Repearl F-7000 and 1.2% Milligard MRX ^TMBe applied to subsequently on this fabric.

This nylon/cotton blended fabric derives from the Milliken Co. in Spartanburg city, the South Carolina.Fabric constitutes 2 * 1 left twill structures by 20/1 RING SPINNING nylon/cotton (52/48) warp thread and 17/1 RING SPINNING nylon/combed cotton (52/48) weft yarn.(below refer in particular to be used for " nylon/cotton blended fabric " of the present invention).Fabric patent face finishing technology, the sandpaper disk of 1000 granularities carries out roughening.Singe then to remove long loose fibres.

Fabric after the processing is measured water and oil-resistant, spray degree, dynamics with preceding method and is rolled the angle, as former state (" AR ").The result lists table 1A in.Fabric after the processing also measure 1 time and 5 home washings after performance, the result lists table 1B respectively in.

Comparative example 23

Nylon/cotton blended fabric

No particle and the arrangement of no matte

With the nylon/cotton blended fabric in the aforementioned one-step method Processing Example 22 (no matte finishing technique).5.0% Repearl F-7000 and 1.2%Milligard MRX ^TMMixture be applied on the fabric.

Embodiment 24

The automobile twills

Face finishing

Two-step method is handled

With the twills of the automobile shown in the aforementioned two-step method Processing Example 4 (with 1200-30-24 level face finishing technology roughening).In the first step of this method, 4.0% Repearl F-7000,1.2% Milligard MRX ^TMBe applied on this fabric with the mixture of 0.1% Wetaid NRW (a kind of wetting agent that can moistening again (non-rewetting) derives from the Noveon Co., Ltd in Cleveland city, Ohio).In second step, 2.5% Ludox CL-P ^TM, 2.5%Milligard MRX and 5.0% Repearl F-7000 mixture be applied to subsequently on this fabric of still hygrometric state.The fabric curing that is dried then.

Embodiment 25

The polyester tent fabric

Face finishing

One-step method is handled

SE-40A with 5% (dimethyl silicone polymer base emulsion, derive from the Kelmar industries company in Duncan city, the South Carolina), according to the surface dressing polyester tent fabric in the aforementioned one-step method Processing Example 6 (with 600-30-12 level face finishing technology roughening).

Residual protective agent is removed in fabric water prewashing (no cleaning agent), and is dry before further testing.The dynamics of measuring fabric with preceding method roll the angle and, be determined as 25 degree.

Embodiment 26

The polyester tent fabric

No matte arrangement

One-step method is handled

Except the polyester tent fabric of surface dressing is not had to repeat embodiment 25 the polyester tent fabric of surface dressing substitutes.Measure the dynamics of fabric with preceding method and roll the angle, survey is greater than 50 degree (limit of tested person instrument)

Embodiment 27

The polyester tent fabric

Face finishing

One-step method is handled

(a kind of zirconium cerul emulsion is as waterproofing agent for Consopel ZW with 5%, derive from the Consos company in Xia Luote city, the South Carolina), according to the surface dressing polyester tent fabric in the aforementioned one-step method Processing Example 6 (with 600-30-12 level face finishing technology roughening).

Measure the dynamics of fabric with preceding method and roll the angle, be determined as 18 degree.

Embodiment 28

The polyester tent fabric

No matte arrangement

One-step method is handled

Except the polyester tent fabric of surface dressing is not had to repeat embodiment 27 the polyester tent fabric of surface dressing substitutes.Measure the dynamics of fabric with preceding method and roll the angle, be determined as 23 degree.

Embodiment 29

Adhesive-bonded fabric

Face finishing

One-step method is handled

Except polyester ship cover fabric is substituted by adhesive-bonded fabric, repeat embodiment 8.The wet pickup of chemistry fabric on this fabric about 78%.

Adhesive-bonded fabric is a spunbond polyester, and every Gram Mass 25 derives from the BBA Nonwovens company in Simpsonville city, the South Carolina.With the 1200-15-6 level, face finishing technology is carried out mechanically roughened with the abrasion roller of coated with CVD (chemical vapor deposition) diamond.

Comparative example 30

Adhesive-bonded fabric

No particle and the arrangement of no matte

Except Sipernat 22LS ^TMComposition repeats embodiment 29 outside being removed from bathe.Without face finishing PROCESS FOR TREATMENT fabric.

Adhesive-bonded fabric after the processing is measured water and oil-resistant, spray degree, dynamics with preceding method and is rolled the angle, as former state (" AR ").The result lists 1A in.

Table 1A barrier propterty test result

Sample	Water proofing property	Grease proofness	The spray degree	Roll digression ^*(degree)
Sample	Water proofing property	Grease proofness	The spray degree	Roll digression ^*(degree)	Embodiment 1	5	5	100	3.0
Embodiment 2	5	5	100	3.5	Embodiment 1	5	5	100	3.0
Embodiment 2	5	5	100	3.5	Comparative example 3	5	5	100	7.0
Embodiment 4	7	7	100	3.5	Comparative example 3	5	5	100	7.0
Embodiment 4	7	7	100	3.5	Comparative example 5	7	6	100	7.0
Embodiment 6	6	6	100	2.0	Comparative example 5	7	6	100	7.0
Embodiment 6	6	6	100	2.0	Comparative example 7	6	6	100	7.2
Embodiment 8	6	6	100	4.0	Comparative example 7	6	6	100	7.2
Embodiment 8	6	6	100	4.0	Comparative example 9	6	6	100	10.0
Embodiment 10	5	5	100	10.0	Comparative example 9	6	6	100	10.0
Embodiment 10	5	5	100	10.0	Comparative example 11	3	4	100	27.0
Comparative example 12	1	0	90	4.5	Comparative example 11	3	4	100	27.0
Comparative example 12	1	0	90	4.5	Comparative example 13	1	0	70	5.0
Comparative example 14	1	0	70	4.5	Comparative example 13	1	0	70	5.0
Comparative example 14	1	0	70	4.5	Comparative example 15	1	0	90	5.4
Comparative example 16	1	0	70	22.5	Comparative example 15	1	0	90	5.4
Comparative example 16	1	0	70	22.5	Embodiment 17	7	6	100	4.5
Embodiment 18	7	6	100	7.0	Embodiment 17	7	6	100	4.5
Embodiment 18	7	6	100	7.0	Embodiment 19	6	6	100	6.5
Embodiment 20	6	6	100	5.0	Embodiment 19	6	6	100	6.5
Embodiment 20	6	6	100	5.0	Comparative example 21	6	6	100	9.5
Embodiment 22	5	5	100	4.7	Comparative example 21	6	6	100	9.5
Embodiment 22	5	5	100	4.7	Comparative example 23	5	5	100	7.0
Embodiment 24	7	6	100	4.9	Comparative example 23	5	5	100	7.0
Embodiment 24	7	6	100	4.9	Embodiment 25	N/A	N/A	N/A	25
Embodiment 26	N/A	N/A	N/A	＞50	Embodiment 25	N/A	N/A	N/A	25
Embodiment 26	N/A	N/A	N/A	＞50	Embodiment 27	N/A	N/A	N/A	18
Embodiment 28	N/A	N/A	N/A	23	Embodiment 27	N/A	N/A	N/A	18
Embodiment 28	N/A	N/A	N/A	23	Embodiment 29	8	6	100	20.0

Sample	Water proofing property	Grease proofness	The spray degree	Roll digression ^*(degree)
Sample	Water proofing property	Grease proofness	The spray degree	Roll digression ^*(degree)	Comparative example 30	8	6	100	38.0

^*: what dynamics was rolled the angle rolls separation from being 3 centimetres

Table 1B: washability test result

Sample	Spray degree (AR)	Dynamics is rolled the angle ^*(degree) (AR)	Spray degree (washing 1 time)	Dynamics is rolled the angle ^*(degree) (washing 1 time)	Spray degree (washing 5 times)	Dynamics is rolled the angle ^*(degree) (washing 5 times)	Spray degree (washing 10 times)	Dynamics is rolled the angle ^*(degree) (washing 10 times)	Spray degree (washing 20 times)	Dynamics is rolled the angle ^*(degree) (washing 20 times)
Sample	Spray degree (AR)	Dynamics is rolled the angle ^*(degree) (AR)	Spray degree (washing 1 time)	Dynamics is rolled the angle ^*(degree) (washing 1 time)	Spray degree (washing 5 times)	Dynamics is rolled the angle ^*(degree) (washing 5 times)	Spray degree (washing 10 times)	Dynamics is rolled the angle ^*(degree) (washing 10 times)	Spray degree (washing 20 times)	Dynamics is rolled the angle ^*(degree) (washing 20 times)	Embodiment 1	100	3.0	90	4.5	75	14	70	18.5	60	26.5
Embodiment 2	100	3.5	100	3.5	100	7.5	100	8.0	100	10.0	Embodiment 1	100	3.0	90	4.5	75	14	70	18.5	60	26.5
Embodiment 2	100	3.5	100	3.5	100	7.5	100	8.0	100	10.0	Embodiment 4	100	3.5	100	7.0	100	13.0	100	18.0	75	23.0
Embodiment 8	100	4.0	100	6.5	90	15.5	85	23.0	85	34.5	Embodiment 4	100	3.5	100	7.0	100	13.0	100	18.0	75	23.0
Embodiment 8	100	4.0	100	6.5	90	15.5	85	23.0	85	34.5	Embodiment 10	100	10.0	70	13.0	10	28.0	10	35.0	N/A	N/A
Comparative example 12	90	4.5	0	wetting	N/ A	N/A	N/ A	N/A	N/A	N/A	Embodiment 10	100	10.0	70	13.0	10	28.0	10	35.0	N/A	N/A
Comparative example 12	90	4.5	0	wetting	N/ A	N/A	N/ A	N/A	N/A	N/A	Comparative example 13	70	5.0	0	wetting	N/ A	N/A	N/ A	N/A	N/A	N/A
Comparative example 14	70	4.5	0	wetting	N/ A	N/A	N/ A	N/A	N/A	N/A	Comparative example 13	70	5.0	0	wetting	N/ A	N/A	N/ A	N/A	N/A	N/A
Comparative example 14	70	4.5	0	wetting	N/ A	N/A	N/ A	N/A	N/A	N/A	Comparative example 15	75	5.4	0	wetting	N/ A	N/A	N/ A	N/A	N/A	N/A
Comparative example 16	85	22.5	0	wetting	N/ A	N/A	N/ A	N/A	N/A	N/A	Comparative example 15	75	5.4	0	wetting	N/ A	N/A	N/ A	N/A	N/A	N/A
Comparative example 16	85	22.5	0	wetting	N/ A	N/A	N/ A	N/A	N/A	N/A	Embodiment 17	100	4.5	N/ A	N/A	100	18.5	85	20.5	80 ^**	22.5 ^**
Embodiment 18	100	7.0	N/ A	N/A	100	19.5	90	24.0	85 ^**	26.5 ^**	Embodiment 17	100	4.5	N/ A	N/A	100	18.5	85	20.5	80 ^**	22.5 ^**
Embodiment 18	100	7.0	N/ A	N/A	100	19.5	90	24.0	85 ^**	26.5 ^**	Embodiment 19	100	6.5	100	9.0	100	N/A	N/ A	N/A	N/A	N/A
Embodiment 20	100	5.0	N/ A	N/A	100	10.5	100	13.0	100 ^**	15.0 ^**	Embodiment 19	100	6.5	100	9.0	100	N/A	N/ A	N/A	N/A	N/A
Embodiment 20	100	5.0	N/ A	N/A	100	10.5	100	13.0	100 ^**	15.0 ^**	Embodiment 22	100	4.5	100	8.0	90	18.0	N/ A	N/A	N/A	N/A
Relatively	100	7.0	90	16.0	70	37.5	N/	N/A	N/A	N/A	Embodiment 22	100	4.5	100	8.0	90	18.0	N/ A	N/A	N/A	N/A

Sample	Spray degree (AR)	Dynamics is rolled the angle ^*(degree) (AR)	Spray degree (washing 1 time)	Dynamics is rolled the angle ^*(degree) (washing 1 time)	Spray degree (washing 5 times)	Dynamics is rolled the angle ^*(degree) (washing 5 times)	Spray degree (washing 10 times)	Dynamics is rolled the angle ^*(degree) (washing 10 times)	Spray degree (washing 20 times)	Dynamics is rolled the angle ^*(degree) (washing 20 times)
Sample	Spray degree (AR)	Dynamics is rolled the angle ^*(degree) (AR)	Spray degree (washing 1 time)	Dynamics is rolled the angle ^*(degree) (washing 1 time)	Spray degree (washing 5 times)	Dynamics is rolled the angle ^*(degree) (washing 5 times)	Spray degree (washing 10 times)	Dynamics is rolled the angle ^*(degree) (washing 10 times)	Spray degree (washing 20 times)	Dynamics is rolled the angle ^*(degree) (washing 20 times)	Example 23	A
Embodiment 24	100	4.9	100	8.5	100	13.0	100	17.0	100	20.0	Example 23	A

^*: what dynamics was rolled the angle rolls separation from being 3 centimetres.

^*: wash 15 times.

" N/A " represents no test data.

Table 1C: wear-resisting wiping test result

Sample	Spray degree (A R)	Dynamics is rolled angle (degree) ^*(AR)	Spray degree (circulating 2000 times)	Dynamics is rolled angle (degree) ^*(circulating 2000 times)	Spray degree (washing 5000 times)	Dynamics is rolled the angle ^*(degree) (washing 5000 times)	Spray degree (washing 10000 times)	Dynamics is rolled the angle ^*(degree) (washing 10000 times)	Spray degree (washing 20000 times)	Dynamics is rolled the angle ^*(degree) (washing 20000 times)
Sample	Spray degree (A R)	Dynamics is rolled angle (degree) ^*(AR)	Spray degree (circulating 2000 times)		Spray degree (washing 5000 times)		Spray degree (washing 10000 times)		Spray degree (washing 20000 times)		Embodiment 1	100	3.0	75	11.0	75	17.0	70	21.5	60	N/A
Embodiment 2	100	3.5	100	12.0	100	16.5	100	20.5	90	N/A	Embodiment 1	100	3.0	75	11.0	75	17.0	70	21.5	60	N/A
Embodiment 2	100	3.5	100	12.0	100	16.5	100	20.5	90	N/A	Embodiment 4	100	3.5	70	N/A	70	N/A	60	N/A	50	N/A
Embodiment 6	100	2.0	70	N/A	70	N/A	70	N/A	50	N/A	Embodiment 4	100	3.5	70	N/A	70	N/A	60	N/A	50	N/A
Embodiment 6	100	2.0	70	N/A	70	N/A	70	N/A	50	N/A	Embodiment 8	100	4.0	75	N/A	75	N/A	70	N/A	70	N/A
Embodiment 10	100	10.0	100	N/A	95	N/A	90	N/A	85	N/A	Embodiment 8	100	4.0	75	N/A	75	N/A	70	N/A	70	N/A
Embodiment 10	100	10.0	100	N/A	95	N/A	90	N/A	85	N/A	Comparative example 12	90	4.5	50	N/A	50	N/A	N/A	N/A	N/A	N/A
Comparative example 13	70	5.0	60	N/A	60	N/A	N/A	N/A	N/A	N/A	Comparative example 12	90	4.5	50	N/A	50	N/A	N/A	N/A	N/A	N/A
Comparative example 13	70	5.0	60	N/A	60	N/A	N/A	N/A	N/A	N/A	Comparative example 14	70	18.0	45	N/A	45	N/A	N/A	N/A	N/A	N/A
Comparative example 15	90	5.4	70	N/A	50	N/A	N/A	N/A	N/A	N/A	Comparative example 14	70	18.0	45	N/A	45	N/A	N/A	N/A	N/A	N/A
Comparative example 15	90	5.4	70	N/A	50	N/A	N/A	N/A	N/A	N/A	Comparative example 16	85	22.5	60	N/A	60	N/A	N/A	N/A	N/A	N/A
Implement	100	4.5	100	28.0	100	33.5	95	N/A	N/A	N/A	Comparative example 16	85	22.5	60	N/A	60	N/A	N/A	N/A	N/A	N/A

Sample	Spray degree (A R)	Dynamics is rolled angle (degree) ^*(AR)	Spray degree (circulating 2000 times)	Dynamics is rolled angle (degree) ^*(circulating 2000 times)	Spray degree (washing 5000 times)	Dynamics is rolled the angle ^*(degree) (washing 5000 times)	Spray degree (washing 10000 times)	Dynamics is rolled the angle ^*(degree) (washing 10000 times)	Spray degree (washing 20000 times)	Dynamics is rolled the angle ^*(degree) (washing 20000 times)
Sample	Spray degree (A R)	Dynamics is rolled angle (degree) ^*(AR)	Spray degree (circulating 2000 times)		Spray degree (washing 5000 times)		Spray degree (washing 10000 times)		Spray degree (washing 20000 times)		Example 17
Embodiment 18	100	7.0	100	30.0	100	35.5	85	N/A	N/A	N/A	Example 17
Embodiment 18	100	7.0	100	30.0	100	35.5	85	N/A	N/A	N/A	Embodiment 19	100	6.5	100	27.5	100	35.0	N/A	N/A	N/A	N/A
Embodiment											Embodiment 19	100	6.5	100	27.5	100	35.0	N/A	N/A	N/A	N/A
Embodiment	20	100	4.5	100	14.0	100	18.0	100	16.5	N/A	N/A
Embodiment 24	20	100	4.5	100	14.0	100	18.0	100	16.5	N/A	N/A	100	4.9	100	16.5	100	20.5	90	25.0	70	30.0

" N/A " represents free of data.

The result of table 1A shows that the fabric after the processing demonstrates good grease-proof and waterproof and excellent spray degree according to the present invention.When comparing with comparative example 11-16, the grease-proof and waterproof of the fabric of handling according to the present invention and spray kilsyth basalt are now excellent unusually.In addition, the fabric of handling according to the present invention shows the dynamics all lower than any comparative example usually and rolls the angle.In addition, embodiment 25-28 has used floride-free chemical protector.Embodiment 25 and 26 uses polysiloxanes as protective agent, and embodiment 27 and 28 uses zirconium wax as protective agent.The lower dynamics of control fabric (using polysiloxanes and wax respectively) that the fabric of surface dressing among the embodiment 25 and 27 (using polysiloxanes and wax respectively) shows than embodiment 26 and 28 is rolled the angle, show that face finishing is handled than handling with protective agent separately can provide the more substrate of waterproof.Embodiment 29 shows that the dynamics that obtains the waterproof adhesive-bonded fabric with the technology among the present invention is rolled the angle than among the embodiment 30, and the same adhesive-bonded fabric of no matte arrangement and particle disposal is much lower.

Therefore, the result of these embodiment shows that advantage that face finishing is handled and nano particle in any interpolation on textile substrates surface, can form and be similar to surface roughness such on the lotus leaf surface, thereby produce the textile substrates with excellent liquid repellent performance.Handle also further give fabric " automatically cleaning " and feature, for example, after undesirable liquid touches textile substrates, be easy to collect together glomeration and roll surface from substrate.

Result among the table 1B shows the fabric after the processing according to the present invention, after the spray degree test through 20 washings, presents good washing fastness usually.11-16 compares with comparative example, and the spray kilsyth basalt of the fabric of handling according to the present invention is now excellent unusually.In addition, the fabric of handling according to the present invention shows the dynamics all lower than any comparative example usually and rolls the angle.More specifically, after washing 1 time, comparative example 12-16 does not show any liquid repellent performance, and most of other embodiment is washing the moderate at least liquid-repellant of maintenance after 20 times.Therefore, the result of these embodiment shows any interpolation on the textile substrates surface of advantage that face finishing is handled and nano particle, formation is similar to surface roughness such on the lotus leaf surface, has wash fast super water proofing property, self-cleaning textile substrates thereby produce.

Result among the table 1C shows the fabric after major part is handled according to the present invention, after through 20000 circulation abrasions, presents good spray degree usually.12-16 compares with comparative example, and the fabric performance of handling according to the present invention is excellent unusually.More particularly, after through 20000 circulations, comparative example 12-16 shows spray degree only in the 45-60 scope, and many fabrics after handling according to the present invention, after circulating through 20000 times, spray degree scope between 50-90-increased four times.In addition, embodiment 1 and 2 is after circulating through 10000 times, show quite low dynamics and roll the angle, embodiment 24 is after circulating through 20000 times, and table quite low dynamics occurs and rolls the angle, therefore, the result shows the fabric after the processing according to the present invention, after standing friction, the friction in for example normal the use can keep water proofing property.Therefore, the result of these embodiment shows any interpolation on the textile substrates surface of advantage that face finishing is handled and nano particle, formation is similar to surface roughness such on the lotus leaf surface, thereby produces the super water proofing property with wear-resisting wiping, self-cleaning textile substrates.

Measure the sample preparation of fiber surface roughness

Representative fiber or yarn from the described fabric sample of embodiment part carefully are placed on the sample platform before microscopic examination.These representative fibers with lotus leaf effect are positioned at the fibre-bearing substrate plane substantially.As following further explanation, measure the coefficient of roughness (R.F.) by the actual physics measurement of fiber.Usually, when being exaggerated big multiple, the coefficient of roughness may have a few height a little, because it is more that the number of individuals that uses in the analytic process can become.Therefore, be amplified to 500 times and be selected as the standard that the textile fabric coefficient of roughness is measured.Calculating based on other multiplication factor only shows sample or concrete point that obtains from document.

Before ESEM detects, carry out metal spraying with Denton Desk II model sputter coating device (New Jersey Morristown city Denton Vacuum Co., Ltd) on these representational fibers or yarn, the gold of about 150 to 200 dusts is deposited to sample surfaces.

Use Amray Model 1845FE ESEM (KLA-Tencor, Inc.160RioRobles, San Jose, California 95134) imaging, under 5 kilovolts of accelerating potentials, operate.

Although 500 times of the most normal use multiplication factors because viewed details the best under this multiple, also can be under various multiplication factors the detection fibers sample.On IBM-compatible personal computer, with WIN TV-GO (Happauge Computer Works, Inc., Happauge, NY) video card construction drawing picture and be saved the image file into jpg, 800 * 600 pixels.

Measure the method for the coefficient of roughness (R.F.)

The coefficient of roughness of representative fibers (R.F.) can be as follows by objective measurement.IMAQ as previously shown.The placement of rough region on the treated fiber of textile substrates (shown in Fig. 7 A) in SEM wanted to make the silhouette of processed fiber high-visible.The fiber surface roughness that is formed by outstanding, scraped finish, particle etc. that fibre finish causes can be clearly seen.What need indicate is, fiber is not an even roughnessization.That is,, may there be roughening away from the side of the fiber of textile substrates top surface although top surface can be by complete roughening at all.On the continuous side of a fiber, measure the fiber coefficient of roughness of fiber top surface.Do not measure on broken fiber end or the tip or near broken fiber end or tip.

Digital picture 800 * 600 pixels that form.Single fiber amplifies 500 times and gathers image.Image file doubly saves as jpeg format 8 byte RGB files.

Fig. 7 A is depicted as the original image from the fiber of the tent fabric described in the embodiment 6 that obtains from ESEM.For seamed edge and the corresponding roughness thereof that focuses on fiber, can extract the parts of images that only shows the coarse seamed edge of processed fiber in the profile.In the image that extracts, the fiber orientation is pointed to one of them limit along image.That direction indication here is the length of image.The length of analyzing the image of usefulness is 100 microns or longer.For example, Fig. 7 B shows the part of extracting the original image of the tent fabric that obtains from Electronic Speculum.

In order to analyze, use two software kits: Adobe Photoshop6.0.1 derives from the Adobe Systems Incorporated company in San Jose city, California; And Image ProPlus4.5, derive from the Media Cybernetics Co., Ltd in Silver Spring city, the Maryland State.The image that extracts converts the grey scale image (every pixel occupies a gray value, from 0 to 255, or from black to white) of 8 bytes at Image Pro Plus4.5.The file that extracts is switched to Adobe Photoshop then.In order to isolate the pixel of image of fiber seamed edge in the expression background, and improve analysis ability, use 3-pixel diameter erase tool to mark boundary between fiber seamed edge and the background.In order to realize this purpose, eraser is configured to change all pixels of crossing in the zone of striding, and simultaneously these pixels is activated to black, and pixel value is 0.Handle the image (on the interface of Adobe Photoshop, amplifying 200% or bigger) be exaggerated with mouse, sketch the contours of boundary between fiber seamed edge and the background exactly, and to set background pixel be 0 with hand.After the pixel of background seamed edge was set to 0, remaining background also was set to 0 (black).

The image the same with Fig. 7 B shown in Fig. 7 C is set to 0 with the said method background.This image in Image Pro Plus, be saved into tiff file as with post analysis.

Use Image Pro Plus, open the black background image file.This image is used to calculate fiber seamed edge roughness.In principle, roughness parameter is defined as fiber seamed edge physical length and comprises that the surface goes up the length (suppose in question this fiber whole length extension along image) of all ledges divided by image.

For the meter facial contour, background pixel can be denoted as black-and-white two color, with the shape (being shade) of display fibers surface roughness.For the meter facial contour, Image Pro Plus allows the user to select some part of image, selects according to the pixel value and the size of this part.Because background pixel has been set to black (pixel value is 0), by being partitioned into the pixel that approaches 0 value, can select background from image.

Because, in image, have shade, there is the pixel value of some pixel objects to approach zero, but do not represent background and profile.These pixel objects always comprise the pixel littler than background.Therefore, be denoted as the background of Pixel Dimensions greater than shade size in the image by requiring the pixel object, the analyst gets rid of shade from profile.

For the purpose of complete, the selection of object wants to make the pixel " hole " in the overall background of selecting pixel to be selected automatically, and mutual contiguous pixel is denoted as background parts in 4 join domains.This means, the object in the image, by have be positioned on the specific pixel under or the neighbours on arbitrary limit, should be connected to the main body in the image; Only the pixel that connects by the diagonal angle will not be included in the selected background object.Be used for the example that Fig. 7 C is labeled background image and be presented at Fig. 7 D.It is the example of the surface roughness image that sketches the contours for Fig. 9 B.The task of handling this image is exactly to measure the length of the background that is connected with fiber, the perhaps length of profile.

In order to measure the length of profile, use the black and white shadow image.By the wide line of single pixel of definition tracking background/fiber line of demarcation seamed edge, estimate interfacial length.Produce the wide line of this list pixel with following method.

At first duplicate shadow image.Handle first copy of shadow image with being called as the morphological filter that corrodes filter.Corrode filter and gather the black-and-white two color image, the line of demarcation of white portion that can mobile image makes image white partly reduce (less pixel), and black partly increases (more pixel), but marginal shape remains unchanged.The shape that corrodes filter is 3 * 3 intersections (cross).This filter is used once on image.Copy with second of the original shadow image of expansion filter process then.This is opposite with the erosion filter.For the image that enlarges, the white portion of image is grown up, and black partly diminishes, and therefore, keeps marginal shape.The expansion filter reuses the filter one time of 3 * 3 X-shapes.Use image algorithm, the absolute difference with the image that enlarges that falls that disappears provides an image, wherein, only keeps single line (wideer than single pixel) on original background/fiber line of demarcation.Because erosion and expansion filter have kept all parts of image, except the boundary zone, this causes identical situation.In order to obtain the wide line of single pixel, use so-called " pruning " filter process absolute difference image once more.This method is gathered the wide line of many pixels and it is compressed to single pixel.Branch on any boundary line all is removed.This final image becomes profile diagram, provides a wide white line of single pixel (pixel value 255), and the roughness profile of fiber is handled in expression.The profile diagram embodiment of Fig. 7 B represents in Fig. 7 E.

The length of the corresponding coarse seamed edge of the coefficient of roughness (R.F.) is directly proportional with the surface roughness that fiber shows usually.Calculate according to definition.Can come contour images is calculated with the computational tool of Image Pro Plus.Computational tool is configured to calculate the white object (pixel value 255) of single pixel of all sizes or big pixel.If many pixels object is above-mentioned four to connect, also meter is made a single body.

Computational tool provides at least two kinds of information.Computational tool provides pixel count on the line of demarcation and the object number on the line of demarcation.Whether the meaning of object relates to again and gets back to pixel is four connections.This length for the computation bound line is important, because when 4 length that connect only are 1 pixel, be 2 along the geometrical length of cornerwise connection (being called 8 connects) ^1/2Pixel.If N object and M pixel are arranged on the line of demarcation, there be N-1 diagonal to connect (length 2 ^1/2), M-N straight line connects (length 1).Therefore, profile (L _P) length (is unit with the pixel) be:

L _p＝(N-1)2 ^1/2+(M-N)。

Image length (L ₁) be simple image pixel length, equal along the sampled length of fiber.This can find at Image Pro Plus, for example by seeing the cylindrical length of bitmap and computed image.The coefficient of roughness of in question this fiber (R.F.) parameter can obtain by calculating the R.F. ratio now:

R.F.＝L _P/L ₁。

Table 1D and 1E list the data of selected sample.The sample number of the data of corresponding table 1A-1C uses in table 1D and 1E equally.For example, " embodiment 2 " are meant the textile substrates according to preparation described in the embodiment 2.In order to compare, the result that the fiber of extracting out from the high rough surface zone of substrate is handled as face finishing, has particle (being shown " FF+ particle " in the table) in its surface, compare with the fiber that extract out in the zone of the surface roughness that does not have face finishing to form, particle (being shown " particle " in the table) is arranged on this fiber surface.

The coefficient of roughness (R.F.) of table 1D embodiment

Sample	Handle	Amplify	Pixel count (N)	Object number (M)	Profile length (L _P)	Image length (L ₁)	R.F.
Sample	Handle	Amplify	Pixel count (N)	Object number (M)	Profile length (L _P)	Image length (L ₁)	R.F.	The lotus leaf effect	Natural	2000	653	325	480	786.21	1.64
Automobile microgroove fabric embodiment 4	The FF+ particle	500	584	231	474	678.27	1.43	The lotus leaf effect	Natural	2000	653	325	480	786.21	1.64
Automobile microgroove fabric embodiment 4	The FF+ particle	500	584	231	474	678.27	1.43	Ship cover fabric embodiment 8	The FF+ particle	500	858	304	771	982.51	1.27
Ship cover fabric embodiment 8	The FF+ particle	500	798	209	771	883.16	1.15	Ship cover fabric embodiment 8	The FF+ particle	500	858	304	771	982.51	1.27
Ship cover fabric embodiment 8	The FF+ particle	500	798	209	771	883.16	1.15	Ship cover fabric embodiment 8	Particle	500	771	75	771	800.65	1.04
Ship cover fabric embodiment 8	Particle	500	772	85	771	805.79	1.05	Ship cover fabric embodiment 8	Particle	500	771	75	771	800.65	1.04
Ship cover fabric embodiment 8	Particle	500	772	85	771	805.79	1.05	Little danier twills embodiment 1	The FF+ particle	500	365	121	300	413.71	1.38
Little danier twills embodiment 1	Particle	500	300	32	300	311.84	1.04	Little danier twills embodiment 1	The FF+ particle	500	365	121	300	413.71	1.38
Little danier twills embodiment 1	Particle	500	300	32	300	311.84	1.04	Little danier twills embodiment 1	Particle	500	300	44	300	316.81	1.06
Fabric Q embodiment 10	The FF+ particle	500	967	331	699	1102.69	1.58	Little danier twills embodiment 1	Particle	500	300	44	300	316.81	1.06
Fabric Q embodiment 10	The FF+ particle	500	967	331	699	1102.69	1.58	Fabric Q embodiment 10	Particle	500	699	74	699	728.24	1.04
Tent fabric embodiment 6	The FF+ particle	500	680	248	594	781.31	1.32	Fabric Q embodiment 10	Particle	500	699	74	699	728.24	1.04
Tent fabric embodiment 6	The FF+ particle	500	680	248	594	781.31	1.32	Tent fabric embodiment 6	Particle	500	594	38	594	608.33	1.02
Tent fabric embodiment 6	The FF+ particle	1000	919	335	717	1056.35	1.47	Tent fabric embodiment 6	Particle	500	594	38	594	608.33	1.02

Sample	Handle	Amplify	Pixel count (N)	Object number (M)	Profile length (L _P)	Image length (L ₁)	R.F.
Sample	Handle	Amplify	Pixel count (N)	Object number (M)	Profile length (L _P)	Image length (L ₁)	R.F.	Tent fabric embodiment 6	Particle	1000	717	56	717	738.78	1.03
Tent fabric embodiment 20	FF	1000	894	424	717	1068.21	1.49	Tent fabric embodiment 6	Particle	1000	717	56	717	738.78	1.03

Table 1E: the coefficient of roughness of comparative example (R.F.)

Sample	Handle	Amplify	Pixel count (N)	Object number (M)	Profile length (L _P)	Image length (L ₁)	R.F.
Sample	Handle	Amplify	Pixel count (N)	Object number (M)	Profile length (L _P)	Image length (L ₁)	R.F.	Automobile twills comparative example 13	Handle according to U.S. Patent application No.2002/ 0016433A1	500	789	150	785	849.72	1.08
Automobile twills comparative example 13	Handle according to U.S. Patent application No.2002/ 0016433A1	500	828	214	785	915.23	1.17 ^*	Automobile twills comparative example 13		500	789	150	785	849.72	1.08
Automobile twills comparative example 13		500	828	214	785	915.23	1.17 ^*	Automobile twills comparative example 13	Handle according to U.S. Patent application No.2002/ 0016433A1	500	790	129	785	842.02	1.07
Automobile twills comparative example 13	Handle according to U.S. Patent application No.2002/ 0016433A1	500	806	143	785	863.82	1.10	Automobile twills comparative example 13		500	790	129	785	842.02	1.07
Automobile twills comparative example 13		500	806	143	785	863.82	1.10	Automobile twills comparative example 13	Handle according to U.S. Patent application No.2002/ 0016433A1	500	860	240	785	958.00	1.22 ^*
Ship cover fabric comparative example 15	Handle according to U.S. Patent application No.2002/ 0016433A1	500	786	142	785	843.40	1.07	Automobile twills comparative example 13		500	860	240	785	958.00	1.22 ^*
Ship cover fabric comparative example 15		500	786	142	785	843.40	1.07	Ship cover fabric comparative example 15	Handle according to U.S. Patent application No.2002/ 0016433A1	500	824	254	785	927.80	1.18 ^*
Ship cover fabric comparative example 15	Handle according to U.S. Patent application No.2002/ 0016433A1	500	785	156	785	848.20	1.08	Ship cover fabric comparative example 15		500	824	254	785	927.80	1.18 ^*
Ship cover fabric comparative example 15		500	785	156	785	848.20	1.08	Ship cover fabric comparative example 15	Handle according to U.S. Patent application No.2002/ 0016433A1	500	794	186	785	869.63	1.11
Little danier twills	According to U.S. Patent application No.2002/	500	785	110	785	829.15	1.06	Ship cover fabric comparative example 15		500	794	186	785	869.63	1.11

Sample	Handle	Amplify	Pixel count (N)	Object number (M)	Profile length (L _P)	Image length (L ₁)	R.F.
Sample	Handle	Amplify	Pixel count (N)	Object number (M)	Profile length (L _P)	Image length (L ₁)	R.F.	Comparative example 12	0016433A1 handles
Little danier twills comparative example 12	Handle according to U.S. Patent application No.2002/ 0016433A1	500	795	117	785	842.05	1.07	Comparative example 12	0016433A1 handles
Little danier twills comparative example 12		500	795	117	785	842.05	1.07	Little danier twills comparative example 12	Handle according to U.S. Patent application No.2002/ 0016433A1	500	620	64	620	645.10	1.04
Little danier twills comparative example 12	Handle according to U.S. Patent application No.2002/ 0016433A1	500	620	69	620	647.17	1.04	Little danier twills comparative example 12		500	620	64	620	645.10	1.04
Little danier twills comparative example 12		500	620	69	620	647.17	1.04	Tent fabric comparative example 14	Handle according to U.S. Patent application No.2002/ 0016433A1	500	619	96	618	657.35	1.06
Tent fabric comparative example 14	Handle according to U.S. Patent application No.2002/ 0016433A1	500	618	118	618	665.46	1.08	Tent fabric comparative example 14		500	619	96	618	657.35	1.06

^*These thundering high coefficient of roughness are considered to be caused by one or more big segregate particle agglomerates on the fiber surface.

Result among table 1D and the 1E shows the fabric that is made of fiber after handling according to the present invention than other super waterproof textile fabric surface of the prior art, and for example, the described fabric in the comparative example shows the higher coefficient of roughness.Coefficient of roughness value has shown that independent use particle manufacturing roughened surface can cause at the processed lip-deep fiber of fabric to have the low coefficient of roughness (RF＜1.10 usually).And in some thundering situations, high coefficient of roughness value can cause that this is not connected on the substrate enduringly by big independent particle agglomerate.Even last three embodiment of table 1D show that the particle that is applied on the fiber surface can not be made significant contribution to the coefficient of roughness as described herein at higher multiplication factor (1000 times).Therefore, as described herein, on the textile substrates surface, can on fiber surface, produce and the similar surface characteristics in lotus leaf surface in conjunction with particle disposal with face finishing, wherein, the coefficient of roughness on surface is more than or equal to 1.10, and shown excellent liquid repellent performance by treated substrate.

Result among the table 1A-1E shows that surface roughness influence is really given the anti-fluidity energy of fibrous substrate, and this can roll angle, high spray degree and high water and oil-resistant by low dynamics and prove.As previously mentioned, surface ratio of the present invention surface of the prior art shows higher and more durable anti-fluidity and self-cleaning property.

According to the data of separating in the table, the present invention has shown that clearly those fabrics with best anti-fluidity, spray degree and washing fastness show the maximum coefficient of roughness.

The present invention can satisfy manufacturing and have the textile substrates of super waterproof and self-cleaning performance, and this substrate goes for many final application.It comprises, is not restricted to this, automobile fabric (for example variable ceiling) and clothes.

Those skilled in the art can make various improvement and modification to the present invention under the situation that does not deviate from scope and spirit of the present invention.In addition, one skilled in the art will recognize that above stated specification only is the mode by embodiment, and do not mean that restriction the described scope of the present invention of claims.

Claims

1. fibre-bearing substrate with first surface and second surface, its at least one surperficial at least a portion has whole microscopic surface texture, wherein said whole microscopic surface texture has the projection that is basically perpendicular to described fibre-bearing substrate plane, and described at least one surface comprises:

(a) have a large amount of parts of the fibers of fracture not substantially, described substantially not the fiber of fracture have along the described fiber surface texture of partial-length at least, the coefficient of roughness of wherein said fiber is more than or equal to 1.10.

2. fibre-bearing substrate as claimed in claim 1, the size of wherein said whole microscopic surface texture is less than 100 microns.

3. fibre-bearing substrate as claimed in claim 1, wherein said whole microscopic surface texture be present in its at least one surface at least 10% on.

4. fibre-bearing substrate as claimed in claim 1, wherein said whole microscopic surface texture be present in its at least one surface at least 15% on.

5. fibre-bearing substrate as claimed in claim 1, wherein said whole microscopic surface texture be present in its at least one surface at least 20% on.

6. fibre-bearing substrate as claimed in claim 1, wherein said fibre-bearing substrate also comprises the protection component on described at least one surface.

7. fibre-bearing substrate as claimed in claim 6, wherein said protection component is selected from chemicals, polysiloxanes, wax and the combination thereof that contains fluorocarbon.

8. fibre-bearing substrate as claimed in claim 7, wherein said protection component is the chemicals that contains fluorocarbon.

9. fibre-bearing substrate as claimed in claim 8, the wherein said chemicals that contains fluorocarbon are the composition of fluorinated acrylate or the composition that contains fluoroethane.

10. fibre-bearing substrate as claimed in claim 6, wherein said fibre-bearing substrate also comprises linked on described at least one surface.

11. fibre-bearing substrate as claimed in claim 10, wherein said linked are the polyurethane-base materials.

12. fibre-bearing substrate as claimed in claim 1, wherein said fibre-bearing substrate also comprises particulate constituent on described at least one surface.

13. fibre-bearing substrate as claimed in claim 12, wherein said particulate constituent comprise that average grain diameter is the particle of 1 nanometer to 50 micron.

14. fibre-bearing substrate as claimed in claim 12, wherein said particulate constituent comprise that average grain diameter is the particle of 5 nanometers to 1 micron.

15. fibre-bearing substrate as claimed in claim 12, wherein said particulate constituent comprise that average grain diameter is the particles of 10 nanometers to 50 nanometers.

16. fibre-bearing substrate as claimed in claim 12, wherein said particulate constituent comprise at least a material that is selected from silicate, doped silicate, ore, silica, polymer, carbon, graphite, slaine, metal dust, silicon dioxide coated metal dust, inorganic oxide and combination thereof.

17. fibre-bearing substrate as claimed in claim 16, wherein said particulate constituent are the silicon-dioxide-substrate materials.

18. fibre-bearing substrate as claimed in claim 17, wherein said silicon-dioxide-substrate material is a cataloid.

19. fibre-bearing substrate as claimed in claim 12, wherein said fibre-bearing substrate also comprises linked on described at least one surface.

20. fibre-bearing substrate as claimed in claim 19, wherein said linked are the polyurethane-base materials.

21. fibre-bearing substrate as claimed in claim 1, wherein said fibre-bearing substrate also comprise protection component, particulate constituent and linked.

22. woven fibre-bearing substrate with first surface and second surface, its at least one surperficial at least a portion has whole microscopic surface texture, wherein said whole microscopic surface texture has the projection that is basically perpendicular to described fibre-bearing substrate plane, and described at least one surface comprises:

(a) have a large amount of parts of the fibers of fracture not substantially, described substantially not the fiber of fracture have along the described fiber surface texture of partial-length at least, the coefficient of roughness of wherein said fiber is more than or equal to 1.10; With

(b) chemical mixture, described chemical mixture comprises:

(i) contain the protection component of fluorocarbon,

(ii) particulate constituent and

(iii) linked;

Wherein, described woven fibre-bearing substrate shows fully durable water proofing property after washing, and when testing, described water proofing property is at least 5 testing II (in May, 1992) according to the 3M waterproof.

23. a manufacturing has the method for the fibre-bearing substrate of first surface and second surface, at least one surperficial at least a portion of this fibre-bearing substrate has whole microscopic surface texture, wherein said whole microscopic surface texture has the projection that is basically perpendicular to described fibre-bearing substrate plane, and described at least one surface comprises:

(i) have a large amount of parts of the fibers of fracture not substantially, described substantially not the fiber of fracture have along the described fiber surface texture of partial-length at least, the coefficient of roughness of wherein said fiber is more than or equal to 1.10;

Said method comprising the steps of:

(a) provide the fibre-bearing substrate, described substrate has first surface and second surface; With

(b) the described at least first surface to described substrate carries out face finishing, forms whole microscopic surface texture thus on described first surface.

24. method as claimed in claim 23, the face finishing of wherein said step (b) is finished by mechanical treatment, chemical treatment or its combination.

25. method as claimed in claim 24, the face finishing of wherein said step (b) is finished by mechanical treatment.

26. method as claimed in claim 25, wherein said mechanical treatment is finished by described at least first surface is contacted with one or more abrasive surfaces.

27. method as claimed in claim 26 is coated with diamond grit or sand paper on wherein said one or more abrasive surfaces.

28. method as claimed in claim 27 is coated with average abrasive grain and is 600 to 1200 diamond grit on the wherein said abrasive surface.

29. method as claimed in claim 28, wherein said abrasive surface comprise one or more abrasion rollers.

30. a manufacturing has the method for the fibre-bearing substrate of first surface and second surface, at least one surperficial at least a portion of described fibre-bearing substrate has whole microscopic surface texture, wherein said whole microscopic surface texture has the projection that is basically perpendicular to described fibre-bearing substrate plane, and described at least one surface comprises:

Said method comprising the steps of:

(a) provide the fibre-bearing substrate, described substrate has first surface and second surface;

(b) the described at least first surface to described substrate carries out face finishing, forms whole microscopic surface texture thus on described first surface; With

(c) chemical mixture is coated on the described at least first surface of described substrate, described chemical mixture comprises the protection component.

31. method as claimed in claim 30, the face finishing of wherein said step (b) is finished by mechanical treatment, chemical treatment or its combination.

32. method as claimed in claim 31, the face finishing of wherein said step (b) is finished by mechanical treatment.

33. method as claimed in claim 32, wherein said mechanical treatment is finished by described at least first surface is contacted with one or more abrasive surfaces.

34. method as claimed in claim 33 is coated with diamond grit or sand paper on wherein said one or more abrasive surfaces.

35. method as claimed in claim 34, being coated with average abrasive grain on the wherein said abrasive surface is 600 to 1200 diamond grits.

36. method as claimed in claim 35, wherein said abrasive surface comprise one or more abrasion rollers.

37. a manufacturing has the method for the fibre-bearing substrate of first surface and second surface, at least one surperficial at least a portion of described fibre-bearing substrate has whole microscopic surface texture, wherein said whole microscopic surface texture has the projection that is basically perpendicular to described fibre-bearing substrate plane, and described at least one surface comprises:

Said method comprising the steps of:

(c) chemical mixture is coated on the described at least first surface of described substrate, described chemical mixture comprises protection component and particulate constituent.

38. a manufacturing has the method for the fibre-bearing substrate of first surface and second surface, at least one surperficial at least a portion of described fibre-bearing substrate has whole microscopic surface texture, wherein said whole microscopic surface texture has the projection that is basically perpendicular to described fibre-bearing substrate plane, and described at least one surface comprises:

Said method comprising the steps of:

(b) the described at least first surface to described substrate carries out face finishing, forms whole microscopic surface texture thus on described first surface;

(c) first chemical mixture is coated on the described at least first surface, described first chemical mixture comprises particulate constituent; With

(d) subsequently, second chemical mixture is coated on the described at least first surface, described second chemical mixture comprises the protection component.

39. a manufacturing has the method for the fibre-bearing substrate of first surface and second surface, at least one surperficial at least a portion of described fibre-bearing substrate has whole microscopic surface texture, wherein said whole microscopic surface texture has the projection that is basically perpendicular to described fibre-bearing substrate plane, and described at least one surface comprises:

(i) have a large amount of parts of broken fiber not substantially, described substantially not the fiber of fracture have along the described fiber surface texture of partial-length at least, the coefficient of roughness of wherein said fiber is more than or equal to 1.10;

Said method comprising the steps of:

(c) first chemical mixture is coated on the described at least first surface, described first chemical mixture comprises the protection component; With

(d) subsequently, second chemical mixture is coated on the described at least first surface, described second chemical mixture comprises protection component and particulate constituent.